CN103154048B - Catalyst system improves impervious fluoropolymer resin with having - Google Patents

Catalyst system improves impervious fluoropolymer resin with having Download PDF

Info

Publication number
CN103154048B
CN103154048B CN201180045712.XA CN201180045712A CN103154048B CN 103154048 B CN103154048 B CN 103154048B CN 201180045712 A CN201180045712 A CN 201180045712A CN 103154048 B CN103154048 B CN 103154048B
Authority
CN
China
Prior art keywords
alternatively
compound
oxide
silica
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201180045712.XA
Other languages
Chinese (zh)
Other versions
CN103154048A (en
Inventor
E·丁
A·P·马西诺
J·L·马丁
Y·于
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Phillips Chemical Co LLC
Original Assignee
Chevron Phillips Chemical Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron Phillips Chemical Co LLC filed Critical Chevron Phillips Chemical Co LLC
Publication of CN103154048A publication Critical patent/CN103154048A/en
Application granted granted Critical
Publication of CN103154048B publication Critical patent/CN103154048B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F11/00Compounds containing elements of Groups 6 or 16 of the Periodic System
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02Ethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/26Polyalkenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/26Polyalkenes
    • B01D71/261Polyethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00Metallocenes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00Metallocene catalysts
    • C08F2420/03Cp or analog not bridged to a non-Cp X ancillary neutral donor

Abstract

Catalyst system, it comprises semi-sandwich chromium complex compound, activator carrier and optional promotor.Formula Cp ' Cr (Cl) 2(L n) compound, wherein Cp ' is η 5-C 5h 4cH 2cH 2cH=CH 2and L npyridine, THF or ether.Formula Cp " Cr (Cl) 2(L n) compound, wherein Cp " is η 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2and L npyridine, THF or ether.

Description

Catalyst system improves impervious fluoropolymer resin with having
The cross reference of related application
The application's theme relate to submit to herein simultaneously and exercise question is the U.S. Patent Application No. 12/890 of " fluoropolymer resin that new catalyst system and having improves impermeability ", 448 [attorney docket 211311US00 (4081-14400)], in order to all objects are incorporated to herein with its entirety by reference.
Background technology
The disclosure relates generally to catalyst system and uses its fluoropolymer resin prepared.More specifically the disclosure relates to the catalyst system comprising half sandwich (half-sandwich) chromium cpd improves impermeability fluoropolymer resin for the preparation of displaying.
Technical field
Due to the combination of polyolefine rigidity, toughness, impermeability, heat impedance, optical characteristics, operability and low cost, they are the plastic materials for the manufacture of various valuable product.One of product of most worthy is plastics film.Especially, PE is one of maximum polymkeric substance consumed in the world.It is multifunctional polymer, provides the high-performance relative to other polymkeric substance and equivalent material such as glass, metal or paper.Plastics film such as PE film is mainly used in packaging application, but they are also for agricultural, medical science and engineering field.
PE thin film fabrication is the various ranks usually distinguished by density polymer, such as, Low Density Polyethylene (LDPE), medium-density polyethylene (MDPE) and high density polyethylene(HDPE) (HDPE), wherein each density range has unique combination of properties, makes it be suitable for specific application.
Although the much positive character of PE, film product is still to moisture (such as, water) and/or gas such as oxygen and carbon dioxide permeable.Therefore, expect to develop the PE film product shown and improve impermeability.The interested catalyst system being exploitation and can producing the fluoropolymer resin that can form the film showing aforementioned desirable properties further.
Invention summary
The catalyst system comprising semi-sandwich chromium complex compound, activator carrier and optional promotor is disclosed herein.
Formula Cp ' Cr (Cl) is disclosed herein further 2(L n) compound, wherein Cp ' is η 5-C 5h 4cH 2cH 2cH=CH 2and L npyridine, THF or ether.
Also " the Cr (Cl) that discloses formula Cp herein 2(L n) compound, wherein Cp " is η 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2and L npyridine, THF or ether.
Accompanying drawing is sketched
Fig. 1 is the figure of the molecular weight distribution of the polymer samples of embodiment 1.
Fig. 2 is the figure of the turning radius as the function of embodiment 1 molecular weight analyte.
Fig. 3 and 4 is figure of the molecular weight distribution of the polymer samples of embodiment 2.
Fig. 5 is the figure of moisture vapour transmission rate as the function of the zero-shear viscosity of embodiment 2 sample.
Detailed Description Of The Invention
The method of the described catalyst composition of catalyst composition and manufacture and use is disclosed herein.In one embodiment, catalyst system comprises transition metal complex, activator carrier, optional other activator and optional promotor.This catalyst system can be used for preparing fluoropolymer resin such as polyolefine.In one embodiment, fluoropolymer resin comprises polyethylene, alternatively high density polyethylene(HDPE).The fluoropolymer resin of type described herein can be formed shows impervious modification and the film that therefore can be particularly useful for food product pack application.Hereafter this fluoropolymer resin is called impervious polymkeric substance (BIP) composition improved.In one embodiment, BIP composition is Natene (such as, multimodal polyethylene homopolymer), and it has herein physical properties and feature in greater detail.
In one embodiment, the method preparing BIP composition makes alpha olefin monomers contact with catalyst system under being included in the condition being applicable to forming desired type polymkeric substance herein.Can use with the polymer-compatible with feature disclosed herein and their any catalyst system can be produced.In one embodiment, catalyst system comprises transition metal complex, activator carrier and optional promotor.
Term " catalyst composition ", " catalyst mixture ", " catalyst system " etc., do not rely on to obtain after component combines from the arrangement (fate) of the contact of component of mixture or the actual product of reaction, the character of catalytic active site or promotor, transition metal complex, for the preparation of any olefinic monomer of pre-contact mixture or activator carrier.So term " catalyst composition ", " catalyst mixture ", " catalyst system " etc. can comprise heterogeneous compositions and homogeneous composition.
With regard to chemical group defined herein, on the one hand, how chemistry " group " can be derived from reference compound or " parent " compound according to this group in form, such as, remove with the microcrith producing group definition from parent compound by formal or describe, even if this group word is not synthesize in like fashion.These groups can be used as substituting group or coordination or are bonded to atoms metal.For example, " alkyl " can be derived from form and remove a hydrogen atom from alkane; " thiazolinyl " is derived from and removes a hydrogen atom from alkene, or alkynyl is derived from and removes a hydrogen atom from alkynes, and " alkylidene group ", " alkenylene " or " alkynylene " can be derived from respectively in form and remove two hydrogen atoms from alkane, alkene or alkynes.And, more upper term can be used for comprising it and is derived from the multiple group removing any amount of (" one or more ") hydrogen atom from parent compound in form, and it can be described as in this example embodiment " alkane group " and it comprises " alkyl ", " alkylidene group " and material according to circumstances needs to have three or more hydrogen atoms removes from alkane.Throughout everywhere, substituting group, part or other chemical parts can form specifically " group " disclose and mean when adopting group as described, follow the chemical structure and bonding rule known.When description group be " coming from ", " being derived from ", " passing through ... formed " or " by ... formed " time, such term in the form meaning uses and does not intend to reflect any concrete synthetic method or program, unless otherwise noted or context need in addition.
The definition of specifying according to IUPAC herein uses term " organic group ": no matter type functional group, has the organic substituent of a free valency at carbon atom.Similarly, " sub-organic group " refers to that the type source of no matter functional group is removed two hydrogen atoms since organic compound or removes two hydrogen atoms from a carbon atom or remove the organic group of a hydrogen atom from each of two different carbon atoms." organic group " refers to the generality group formed by removing one or more hydrogen atom from the carbon atom of organic compound.Therefore, " organic group ", " sub-organic group " and " organic group " can comprise organo-functional group (one or more) outside de-carbon and hydrogen and/or atom (one or more), that is, the organic group that functional group and/or de-carbon and hydrogen also have atom outward can be comprised.Such as, the non-limitative example of the atom outside de-carbon and hydrogen comprises halogen, oxygen, nitrogen, phosphorus etc.The non-limitative example of functional group comprises ether, aldehyde, ketone, ester, sulfide, amine etc.On the one hand; be removed to form " organic group ", the hydrogen atom (one or more) of " sub-organic group " or " organic group " can be connected to the carbon atom belonging to functional group, functional group is acyl group (-C (O) R), formyl radical (-C (O) H), carboxyl (-C (O) OH), alkyloxycarbonyl group (hydrocarboxycarbonyl group) (-C (O) OR), cyano group (-C ≡ N), formamyl (-C (O) NH such as 2), N-hydrocarbylamino formyl radical (-C (O) NHR) or N, N'-Dialkylamino formyl radical (-C (O) NR 2) and other possible groups.On the other hand, be removed to form " organic group ", the hydrogen atom (one or more) of " sub-organic group " or " organic group " can be connected to and not belong to functional group and the carbon atom away from functional group, described functional group such as-CH 2c (O) CH 3,-CH 2nR 2, etc." organic group ", " sub-organic group " or " organic group " can be comprise ring-type or acyclic aliphatic series or can be aromatic." organic group ", " sub-organic group " and " organic group " also comprise containing heteroatomic ring, containing heteroatomic loop systems, assorted aromatic nucleus and assorted aromatic nucleus system." organic group ", " sub-organic group " and " organic group " can be direct-connected or branches, unless otherwise noted.Finally, it should be noted that, " organic group ", " sub-organic group " or " organic group " definition comprise " alkyl ", " alkylene ", " hydrocarbyl group " respectively, and comprise " alkyl ", " alkylidene group " and " alkane group " respectively as member.
Definition according to IUPAC specifies: remove monoradical that hydrogen atom the formed group of carbon containing and hydrogen (that is, only) from hydrocarbon, use term " alkyl " herein.The limiting examples of alkyl comprises ethyl, phenyl, tolyl, propenyl etc.Similarly, " alkylene " refers to the group removing two hydrogen atoms formation from hydrocarbon---from a carbon atom, remove two hydrogen atoms or each removal hydrogen atom from two different carbon atoms.Therefore, according to term used herein, " alkyl " refers to remove from hydrocarbon the generality group that one or more hydrogen atom (needs according to special groups) formed." alkyl ", " alkylene " and " hydrocarbyl group " can be acyclic or cyclic group, and/or straight chain or branch." alkyl ", " alkylene " and " hydrocarbyl group " can comprise ring, loop systems, aromatic ring and aromatic ring system, and it is carbon containing and hydrogen only.Such as, " alkyl ", " alkylene " and " hydrocarbyl group " comprise aryl, arylidene, aromatic hydrocarbon group, alkyl, alkylidene group, alkane group, cycloalkyl, cycloalkylidene, naphthenic hydrocarbon group, aralkyl, sub-aralkyl and aralkyl hydrocarbyl group etc. respectively as member.
Definition according to IUPAC specifies: the monoradical removing a hydrogen atom formation from alkane, uses term " alkyl " herein.Similarly, " alkylidene group " refers to the group (remove two hydrogen atoms or remove a hydrogen atom from two different carbon atoms from a carbon atom) removing two hydrogen atoms formation from alkane." alkane group " refers to the generic term by removing the group that one or more hydrogen atom (needs according to special groups) is formed from alkane." alkyl ", " alkylidene group " and " groups " can be acyclic or ring-types, and/or can be straight chain or branch, unless otherwise noted.Primary, secondary and tertiary alkyl is removed hydrogen atom obtain respectively by primary, secondary, the tertiary carbon atom from alkane.Alkyl is obtained by removing hydrogen atom from the terminal carbon of straight-chain paraffin.Radicals R CH 2(R ≠ H), R 2cH (R ≠ H) and R 3c (R ≠ H) is primary, secondary and tertiary alkyl respectively.
In one embodiment, the catalyst system preparing BIP comprises the product of contact of transition metal complex, activator carrier and optional promotor.Transition metal complex can be represented by following general formula
M(Z)(R 1)(R 2)L n
Wherein M is transition metal, alternatively chromium, and Z, R 1and R 2the part with M coordination, and L nbe neutral donor group, wherein n is 0,1 or 2.In another embodiment, L ncan be THF, acetonitrile, pyridine, ether or dipyridyl.In one embodiment, Z comprises η 3to η 5-cyclopentadienyl moieties.Be suitable for η of the present disclosure 3to η 5the non-limitative example of-cyclopentadienyl moieties comprises cyclopentadienyl ligands, indenyl ligands, fluorenyl ligand etc., derivative that is that comprise these any one fractional saturation or that replace or analogue.Substituting group possible on these parts comprises hydrogen, and description therefore in the disclosure " its derivative replaced " comprises the fluorenyl etc. of the indenyl of part such as tetrahydro indenyl, tetrahydrofluorenyl, octahydrofluorenyl, the fractional saturation of fractional saturation, the fluorenyl of fractional saturation, the indenyl of the fractional saturation of replacement, the fractional saturation of replacement.In one embodiment, Z comprises cyclopentadienyl moieties and transition metal complex is called as " half sandwich complex ".Cyclopentadienyl moieties can be characterized by formula below:
In one embodiment, each R of cyclopentadienyl moieties can be different.In some embodiments, each R can be identical.In one embodiment, each R can independently selected from hydrogen, organic group; Or alternatively, hydrogen and alkyl.In embodiments, each R can be H or C independently 1to C 20organic group; Alternatively, H or C 1to C 10organic group; Or alternatively, H or C 1to C 5organic group.In other embodiments, each R can be H or C independently 1to C 20alkyl; Alternatively, H or C 1to C 10alkyl; Or alternatively, H or C 1to C 5alkyl or alternatively H.In one embodiment, R can be C 1to C 60sub-organic group; Alternatively, C 1to C 50sub-organic group; Alternatively, C 1to C 40sub-organic group; Alternatively, C 1to C 30sub-organic group; Or alternatively, C 1to C 20sub-organic group.In other embodiments, each R can be C independently 1to C 60alkylene; Alternatively, C 1to C 50alkylene; Alternatively, C 1to C 40alkylene; Alternatively, C 1to C 30alkylene; Alternatively, C 1to C 20alkylene.
In some embodiments, each non-hydrogen R group can be alkyl independently.In one embodiment, the alkyl that can be used as non-hydrogen R group can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or nonadecyl; Or alternatively, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, or decyl.In some embodiments, the alkyl that can be used as non-hydrogen R group can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl or neo-pentyl; Alternatively, methyl, ethyl, sec.-propyl, the tertiary butyl, or neo-pentyl; Alternatively, methyl; Alternatively, ethyl; Alternatively, n-propyl; Alternatively, sec.-propyl; Alternatively, the tertiary butyl; Or alternatively, neo-pentyl.
In one embodiment, each R can be alkylidene group independently, alternatively, and alkenylene.Such as, each R can be methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-tridecyl, sub-tetradecyl, sub-pentadecyl, sub-hexadecyl, sub-heptadecyl, sub-octadecyl or sub-nonadecyl independently; Or alternatively, methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl.In some embodiments, each R can be methylene radical, ethylidene, propylidene, butylidene or pentylidene independently.In other embodiments, each R can be methylene radical independently; Alternatively, ethylidene; Alternatively, propylidene; Alternatively, butylidene; Alternatively, pentylidene; Alternatively, hexylidene; Alternatively, sub-heptyl; Alternatively, octylene; Alternatively, nonamethylene; Alternatively, sub-decyl; Alternatively, sub-undecyl; Alternatively, sub-dodecyl; Alternatively, sub-tridecyl; Alternatively, sub-tetradecyl; Alternatively, sub-pentadecyl; Alternatively, sub-hexadecyl; Alternatively, sub-heptadecyl; Alternatively, sub-octadecyl; Or alternatively, sub-nonadecyl.In some embodiments, each R can be sub-second-1,2-base, sub-third-1,3-base, Aden-Isosorbide-5-Nitrae-Ji, Aden-2,3-base, sub-penta-1,5-base, 2,2-dimethyl Asia third-1,3-bases, sub-own-1,6-base or 2,3-dimethyl Aden-2,3-base independently; Alternatively, sub-second-1,2-base, sub-third-1,3-base, Aden-Isosorbide-5-Nitrae-Ji, sub-penta-1,5-base or sub-own-1,6-base; Alternatively, sub-second-1,2-base; Alternatively, sub-third-1,3-base; Alternatively, Aden-Isosorbide-5-Nitrae-Ji; Alternatively, Aden-2,3-base; Alternatively, sub-penta-1,5-base; Alternatively, 2,2-dimethyl Asia third-1,3-base; Alternatively, sub-own-1,6-base; Or alternatively, 2,3-dimethyl Aden-2,3-base.
In one embodiment, each R can be vinylidene, propenylidene, crotonylidene, inferior pentenyl, sub-hexenyl, sub-heptenyl, sub-octenyl, sub-nonene base, sub-decene base, sub-hendecene base, sub-laurylene base, sub-tridecylene base, sub-tetradecene base, sub-ten pentaene bases, sub-hexadecylene base, sub-17 thiazolinyls, sub-octadecylene base or sub-19 thiazolinyls independently; Or alternatively, vinylidene, propenylidene, crotonylidene, inferior pentenyl, sub-hexenyl, sub-heptenyl, sub-octenyl, sub-nonene base, sub-decene base.In some embodiments, each R can be vinylidene, propenylidene, crotonylidene or inferior pentenyl independently.In other embodiments, each R can be vinylidene independently; Alternatively, propenylidene; Alternatively, crotonylidene; Alternatively, inferior pentenyl; Alternatively, sub-hexenyl; Alternatively, sub-heptenyl; Alternatively, sub-octenyl; Alternatively, sub-nonene base; Alternatively, sub-decene base; Alternatively, sub-hendecene base; Alternatively, sub-laurylene base; Alternatively, sub-tridecylene base; Alternatively, sub-tetradecene base; Alternatively, sub-ten pentaene bases; Alternatively, sub-hexadecylene base; Alternatively, sub-17 thiazolinyls; Alternatively, sub-octadecylene base; Or alternatively, sub-19 thiazolinyls.Generally speaking, the carbon-to-carbon double bond (one or more) of any alkenylene disclosed herein can be positioned at any position of alkenylene.In one embodiment, alkenylene comprises end carbon-to-carbon double bond.
In one embodiment, each R of cyclopentadienyl comprises alkyl, alternatively, and methyl.In one embodiment, Z comprises pentamethylcyclopentadiene base, hereinafter referred to as Cp*.In another embodiment, at least one R of cyclopentadienyl comprises sub-organic group, alkylene alternatively.In one embodiment, cyclopentadienyl comprises Bao Han – C (CH 3) 2cH 2cH 2cH=CH 2a R group, and all the other R group comprise hydrogen, hereinafter referred to as Cp '.Cyclopentadienyl comprises Bao Han – CH alternatively 2cH 2cH=CH 2a R group, and all the other R group comprise hydrogen and hereinafter referred to as Cp ".Cp ' and Cp " any appropriate means can be used to prepare.Such as, suitable preparation method is at Brieger etc., J.Org.Chem.36 (1971) p243; Bochmann etc., J.Organmet.Chem.592 (1999); Theopold etc., J.Am.Chem.Soc.111 (1989) p9127; With Fendrick etc., Inorg.Synth., describe in 29 (1992) p193, its each section is incorporated to herein with its entirety by reference.
R in one embodiment 1and R 2can be different.In other embodiments, R 1and R 2can be identical.In one embodiment, R 1and R 2each can independently selected from halogen root, organic group or alkyl.In embodiments, R 1and R 2each can be halogen root, C independently 1to C 20organic group; Alternatively, C 1to C 10organic group; Or alternatively, C 1to C 5organic group.In other embodiments, R 1and R 2each can be halogen root, C independently 1to C 20alkyl; Alternatively, C 1to C 10alkyl; Or C alternatively 1to C 5alkyl.
In some embodiments, R 1and R 2each can independently selected from the heteroaryl of the aryl of the cycloalkyl of halogen root, alkyl, cycloalkyl, replacement, aryl, replacement, heteroaryl and replacement.In other embodiments, R 1and R 2each can be the aryl of halogen root, alkyl, cycloalkyl, the cycloalkyl of replacement, aryl or replacement independently; Alternatively, halogen root; Alkyl alternatively; Alternatively, the cycloalkyl of cycloalkyl or replacement; Alternatively, the aryl of aryl or replacement; Or alternatively, the heteroaryl of heteroaryl or replacement.In still other embodiments, R 1and R 2each can be halogen root independently, alternatively, alkyl; Alternatively, cycloalkyl; Alternatively, the cycloalkyl of replacement; Alternatively, aryl; Alternatively, the aryl of replacement; Alternatively, heteroaryl; Or alternatively, the heteroaryl of replacement.
In one embodiment, R 1and R 2each can be fluorine root, chlorine root, bromine root or iodine root independently; Alternatively, fluorine root or chlorine root; Alternatively, chlorine root.In some embodiments, R 1and R 2at least two be halogen root; Alternatively, R 1and/or R 2for chlorine root.
In one embodiment, can be used as R 1and/or R 2the alkyl of group can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or nonadecyl; Or alternatively, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl or decyl.In some embodiments, can be used as R 1and/or R 2the alkyl of group can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl or neo-pentyl; Alternatively, methyl, ethyl, sec.-propyl, the tertiary butyl or neo-pentyl; Alternatively, methyl; Alternatively, ethyl; Alternatively, n-propyl; Alternatively, sec.-propyl; Alternatively, the tertiary butyl; Or alternatively, neo-pentyl.
In one embodiment, can be used as R 1and/or R 2the cycloalkyl of group can be the ring octyl group of cyclobutyl, the cyclobutyl of replacement, cyclopentyl, the cyclopentyl of replacement, cyclohexyl, the cyclohexyl of replacement, suberyl, the suberyl of replacement, ring octyl group or replacement.In some embodiments, can be used as R 1and/or R 2the cycloalkyl of group can be the cyclohexyl of cyclopentyl, the cyclopentyl of replacement, cyclohexyl or replacement.In other embodiments, can be used as R 1and/or R 2the cycloalkyl of group can be the cyclobutyl of cyclobutyl or replacement; Alternatively, the cyclopentyl of cyclopentyl or replacement; Alternatively, the cyclohexyl of cyclohexyl or replacement; Alternatively, the suberyl of suberyl or replacement; Or alternatively, ring octyl group, or the ring octyl group replaced.In further embodiment, can be used as R 1and/or R 2the cycloalkyl of group can be cyclopentyl; Alternatively, the cyclopentyl of replacement; Cyclohexyl; Or alternatively, the cyclohexyl of replacement.Disclose the substituting group of the cycloalkyl of replacement herein independently and unrestrictedly can be can be used as R for further describing 1and/or R 2the cycloalkyl of the replacement of group.
In an aspect, can be used as R 1and/or R 2the aryl (one or more) of group can be the naphthyl of phenyl, the phenyl of replacement, naphthyl or replacement.In one embodiment, can be used as R 1and/or R 2the aryl (one or more) of group can be the phenyl of phenyl or replacement; Alternatively, the naphthyl of naphthyl or replacement; Alternatively, phenyl or naphthyl; Or alternatively, the phenyl of replacement or the naphthyl of replacement.
In one embodiment, can be used as R 1and/or R 2phenyl, 2,4-dibasic phenyl, 2,6-dibasic phenyl, 3,5-dibasic phenyl or 2,4,6-trisubstd phenyl that the phenyl that the phenyl of the replacement of group can be phenyl that 2-replaces, 3-replaces, 4-replace.In other embodiments, can be used as R 1and/or R 2the phenyl of the replacement of group can be phenyl that 2-replaces, 4-replaces phenyl, 2,4-dibasic phenyl or the dibasic phenyl of 2,6-; Alternatively, 3-replace phenyl or the dibasic phenyl of 3,5-; Alternatively, the phenyl of 2-replacement or the phenyl of 4-replacement; Alternatively, the dibasic phenyl of 2,4-or the dibasic phenyl of 2,6-; Alternatively, the phenyl of 2-replacement; Alternatively, the phenyl of 3-replacement; Alternatively, the phenyl of 4-replacement; Alternatively, the dibasic phenyl of 2,4-; Alternatively, the dibasic phenyl of 2,6-; Alternatively, the dibasic phenyl of 3,5-; Or alternatively, 2,4,6-trisubstd phenyl.
In one embodiment, can be used as R 1and/or R 2each non-hydrogen substituent (one or more) of the heteroaryl of the cycloalkyl of the replacement of group, the aryl of replacement or replacement can independently selected from halogen root, C 1to C 10alkyl or C 1to C 10-oxyl; Alternatively, halogen root or C 1to C 10alkyl; Alternatively, halogen root or C 1to C 10-oxyl; Alternatively, C 1to C 10alkyl or C 1to C 10-oxyl; Alternatively, halogen root; Alternatively, C 1to C 10alkyl; Or alternatively, C 1to C 10-oxyl.In some embodiments, can be used as R 1and/or R 2each non-hydrogen substituent (one or more) of the heteroaryl of the cycloalkyl of the replacement of group, the aryl of replacement or replacement can independently selected from halogen root, C 1to C 5alkyl or C 1to C 5-oxyl; Alternatively, halogen root or C 1to C 5alkyl; Alternatively, halogen root or C 1to C 5-oxyl; Alternatively, C 1to C 5alkyl or C 1to C 5-oxyl; Alternatively, halogen root; Alternatively, C 1to C 5alkyl; Or alternatively, C 1to C 5-oxyl.Disclose concrete substituting group halogen root, alkyl and-oxyl herein independently and unrestrictedly can be can be used as R for further describing 1and/or R 2the substituting group of the heteroaryl of the cycloalkyl of the replacement of group, the aryl of replacement or replacement.
In one embodiment, the cycloalkyl (general or concrete) of replacement, the aryl (general or concrete) replaced, any halogen root substituting group of heteroaryl (general or concrete) of replacing can be fluorine root, chlorine root, bromine root or iodine root; Alternatively, fluorine root or chlorine root.In some embodiments, the cycloalkyl (general or concrete) of replacement, the aryl (general or concrete) replaced, any halogen root substituting group of heteroaryl (general or concrete) of replacing can be fluorine root; Alternatively, chlorine root; Alternatively, bromine root; Or alternatively, iodine root.
In one embodiment, the cycloalkyl (general or concrete) of replacement, the aryl (general or concrete) replaced or any hydrocarbyl substituent of heteroaryl (general or concrete) of replacing can be alkyl, aryl or aralkyl; Alternatively, alkyl; Alternatively, aryl, or aralkyl.Generally speaking, alkyl, aryl and aralkyl substituents can have the carbonatoms identical with hydrocarbyl substituent disclosed herein.In one embodiment, the cycloalkyl (general or concrete) of replacement, the aryl (general or concrete) replaced, any alkyl substituent of heteroaryl (general or concrete) of replacing can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, 2-amyl group, 3-amyl group, 2-methyl-1-butene base, tert-pentyl, 3-methyl isophthalic acid-butyl, 3-methyl-2-butyl or neo-pentyl; Alternatively, methyl, ethyl, sec.-propyl, the tertiary butyl or neo-pentyl; Alternatively, methyl; Alternatively, ethyl; Alternatively, sec.-propyl; Alternatively, the tertiary butyl; Or alternatively, neo-pentyl.In one embodiment, the cycloalkyl (general or concrete) replaced, the aryl replaced (general or concrete), any aryl substituent of heteroaryl (general or concrete) replaced can be phenyl, tolyl, xylyl or 2,4,6-trimethylphenyl; Alternatively, phenyl; Alternatively, tolyl, alternatively, xylyl; Or alternatively, 2,4,6-trimethylphenyl.In one embodiment, the cycloalkyl (general or concrete) of replacement, the aryl (general or concrete) replaced, any aralkyl substituents of heteroaryl (general or concrete) of replacing are phenmethyl.
In one embodiment, the cycloalkyl (general or concrete) of replacement, the aryl (general or concrete) replaced, any-oxyl substituting group of heteroaryl (general or concrete) of replacing can be alkoxyl group, aryloxy or and aralkoxy; Alternatively, alkoxyl group; Alternatively, aryloxy, or aralkoxy.Generally speaking, alkoxyl group, aryloxy and aralkoxy substituting group can have the carbonatoms identical with-oxyl substituting group disclosed herein.In one embodiment, the cycloalkyl (general or concrete) of replacement, the aryl (general or concrete) replaced, any alkoxy substituent of heteroaryl (general or concrete) of replacing can be methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2-methyl-1-butene oxygen base, tertiary pentyloxy, 3-methyl isophthalic acid-butoxy, 3-methyl-2-butoxy or neopentyl oxygen; Alternatively, methoxyl group, oxyethyl group, isopropoxy, tert.-butoxy or neopentyl oxygen; Alternatively, methoxyl group; Alternatively, oxyethyl group; Alternatively, isopropoxy; Alternatively, tert.-butoxy; Or alternatively, neopentyl oxygen.In one embodiment, the cycloalkyl (general or concrete) replaced, the aryl replaced (general or concrete), any aryloxy substituting group of heteroaryl (general or concrete) replaced can be phenoxy group, tolyloxy, xylyloxy or 2,4,6-trimethylammonium phenoxy group; Alternatively, phenoxy group; Alternatively, tolyloxy, alternatively, xylyloxy; Or alternatively, 2,4,6-trimethylammonium phenoxy group.In one embodiment, the cycloalkyl (general or concrete) of replacement, the aryl (general or concrete) replaced, any aralkoxy substituting group of heteroaryl (general or concrete) of replacing can be benzoyloxy.
In one embodiment, be suitable for transition metal complex of the present disclosure comprise such as formula I represent Cp*Cr (CH 3) 2(py).
In one embodiment, be suitable for transition metal complex of the present disclosure and comprise the Cp ' Cr (Cl) represented such as formula II 2(THF).
In one embodiment, be suitable for transition metal complex of the present disclosure and comprise Cp as formula III represents " Cr (Cl) 2(THF).
Alternatively, catalyst system comprises more than a kind of transition metal complex.
The catalyst system of preparation BIP can comprise activator carrier further.The disclosure comprises the various catalyst compositions containing the activator that can be activator carrier.On the one hand, activator carrier comprises chemically treated soild oxide.Alternatively, activator carrier can comprise clay mineral, column clay, the clay of stripping, gel to the silicate minerals of the silicate minerals of the clay of the stripping in another oxide matrix, layering, non-layered, the pure aluminium silicate mineral of layering, the pure aluminium silicate mineral of non-layered or its arbitrary combination.
Generally speaking, compared with corresponding untreated solid oxide, chemically treated soild oxide shows the acidity strengthened.Compared with corresponding untreated solid oxide, chemically treated soild oxide is also used as catalyst activator.Although the chemically treated soild oxide activating metallocenes (one or more) when there is not promotor, there is no need to remove promotor from catalyst composition.Compared with comprising the catalyst composition of corresponding untreated soild oxide, the mobilizing function of activator carrier is obvious in the increased activity of catalyst composition generally.But, even if believe when lack organo-aluminium compound, aikyiaiurnirsoxan beta, organic boron or organoborate compound, ionizing ionic compounds etc., chemically treated soild oxide also can be used as activator.
Chemically treated soild oxide can comprise the soild oxide by electrophilic anionic treatments.Although do not intend by following statement restriction, the soild oxide of phase credit electrophilic component process increases or strengthens the acidity of oxide compound.Therefore, activator carrier is shown and is usually greater than the Louis of untreated soild oxide or the Louis of Bronsted strength of acid or Bronsted acidity, or activator carrier has the acid sites of greater amt than untreated soild oxide, or both have.A kind of method quantizing the acidity of chemically treated and untreated solid oxide material be by compare process with the polymerization activity of untreated oxide compound under acid catalyzed reaction.
Chemically treated soild oxide of the present disclosure is generally by showing lewis acidity or Bronsted acidity behavior and the inoganic solids oxide compound with relative high porosity is formed.Soild oxide electrophilic component, the typically chemical treatment of electrophilic negatively charged ion, to form activator carrier.
According to one side of the present disclosure, the soild oxide for the preparation of chemically treated soild oxide has pore volume and is greater than about 0.1cc/g.According to another aspect of the present disclosure, the pore volume of soild oxide is greater than about 0.5cc/g.According to still another aspect of the present disclosure, the pore volume of soild oxide is greater than about 1.0cc/g.
On the other hand, the surface-area of soild oxide is from about 100 to about 1000m 2/ g.Still on the other hand, the surface-area of soild oxide is from about 200 to about 800m 2/ g.In still another aspect of the present disclosure, the surface-area of soild oxide is from about 250 to about 600m 2/ g.
Chemically treated soild oxide can comprise solid inorganic oxide, and it comprises oxygen and is selected from one or more elements of periodictable the 2nd race, the 3rd race, the 4th race, the 5th race, the 6th race, the 7th race, the 8th race, the 9th race, the 10th race, the 11st race, the 12nd race, the 13rd race, the 14th race or the 15th race; Or they one or more elements comprising oxygen and be selected from group of the lanthanides or actinium series are (see Hawley's Condensed Chemical Dictionary, 11 thed., John Wiley & Sons, 1995; Cotton, F.A., Wilkinson, G., Murillo, C.A., and Bochmann, M., Advanced Inorganic Chemistry, 6 thed., Wiley-Interscience, 1999).Such as, inorganic oxide can comprise oxygen and be selected from one or more elements of Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn and Zr.
The suitable example that can be used for the solid oxide material or compound forming chemically treated soild oxide includes but not limited to Al 2o 3, B 2o 3, BeO, Bi 2o 3, CdO, Co 3o 4, Cr 2o 3, CuO, Fe 2o 3, Ga 2o 3, La 2o 3, Mn 2o 3, MoO 3, NiO, P 2o 5, Sb 2o 5, SiO 2, SnO 2, SrO, ThO 2, TiO 2, V 2o 5, WO 3, Y 2o 3, ZnO, ZrO 2deng, comprise the oxide compound of its mixing, and its combination.Such as, soild oxide can comprise silicon-dioxide, aluminum oxide, silica-alumina, the aluminum oxide of coating silica, aluminum phosphate, aluminate or phosphate, heteropoly tungstates, titanium oxide, zirconium white, magnesium oxide, boron oxide, zinc oxide, its oxide compound mixed, or its arbitrary combination.
Soild oxide of the present disclosure comprises oxide material, such as aluminum oxide, its " oxide compound of mixing " compound, such as silica-alumina, and its combination and mixture.The oxide compound of mixing, such as silica-alumina, can be single or multiple chemofacies, to be wherein combined with oxygen more than a kind of metal and to form solid oxide.The example that can be used for the oxide compound of the mixing of disclosure activator carrier includes but not limited to silica-alumina, silica-titania, silica-zirconium oxide, zeolite, various clay mineral, aluminium oxide-titanium oxide, aluminium oxide-zirconium oxide, zinc-aluminate, alumina-boron oxide, silica-boria, aluminate or phosphate-silicon-dioxide, titania-zirconia etc.Soild oxide of the present disclosure also comprises oxide material, the aluminum oxide of such as coating silica, and described in U.S. Patent Application No. 2010-0076167, its content is incorporated to herein with its entirety by reference.
Electrophilic component for the treatment of soild oxide can be the Louis of process rear increase soild oxide or any component of Bronsted acidity (compared with not using the soild oxide of at least one electrophilic anionic treatments).According to one side of the present disclosure, electrophilic component is derived from the electrophilic negatively charged ion as the salt of this source of anions or precursor, acid or other compounds such as volatile organic compounds.The example of electrophilic negatively charged ion includes but not limited to sulfate radical, bisulfate ion, fluorine root, chlorine root, bromine root, iodine root, fluorosulfuric acid root, fluoroboric acid root, phosphate radical, hexafluorophosphoric acid root, trifluoroacetic acid root, trifluoromethanesulfonic acid root, fluorine zirconate, hydrofluotitanic acid root, phospho-wolframic acid root etc., comprises its mixture and combination.In addition, the disclosure also can adopt other ions as these electrophilic source of anions or non-ionic compound.More of the present disclosure in, consider that electrophilic negatively charged ion can be maybe can comprise, fluorine root, chlorine root, bromine root, phosphate radical, trifluoromethanesulfonic acid root, bisulfate ion or sulfate radical etc., or its arbitrary combination.In other respects, electrophilic negatively charged ion can comprise sulfate radical, bisulfate ion, fluorine root, chlorine root, bromine root, iodine root, fluorosulfuric acid root, fluoroboric acid root, phosphate radical, hexafluorophosphoric acid root, trifluoracetic acid root, trifluoromethanesulfonic acid root, fluorine zirconate, hydrofluotitanic acid root etc., or its arbitrary combination.
Therefore, such as, for disclosure catalyst composition (such as, BIP) activator carrier (such as, chemically treated soild oxide) can be, maybe can comprise the aluminum oxide fluoridized, the aluminum oxide of chlorination, the aluminum oxide of bromination, Sulfated aluminum oxide, the silica-alumina fluoridized, the silica-alumina of chlorination, the silica-alumina of bromination, Sulfated silica-alumina, the silica-zirconium oxide fluoridized, the silica-zirconium oxide of chlorination, the silica-zirconium oxide of bromination, Sulfated silica-zirconium oxide, the silica-titania fluoridized, the aluminum oxide of the coating silica fluoridized, the aluminum oxide of Sulfated coating silica, the aluminum oxide etc. of the coating silica of phosphorylation, or its combination.On the one hand, activator carrier can be, maybe can comprise, aluminum oxide of the aluminum oxide fluoridized, Sulfated aluminum oxide, the silica-alumina fluoridized, Sulfated silica-alumina, the aluminum oxide of coating silica fluoridized, the aluminum oxide of Sulfated coating silica, the coating silica of phosphorylation etc. or its arbitrary combination.On the other hand, activator carrier comprises the aluminum oxide fluoridized; Alternatively, the aluminum oxide of chlorination is comprised; Alternatively, Sulfated aluminum oxide is comprised; Alternatively, the silica-alumina fluoridized is comprised; Alternatively, Sulfated silica-alumina is comprised; Alternatively, the silica-zirconium oxide fluoridized is comprised; Alternatively, the silica-zirconium oxide of chlorination is comprised; Or alternatively, comprise the aluminum oxide of the coating silica fluoridized.
When electrophilic component comprises the salt of electrophilic negatively charged ion, the counter ion of this salt or positively charged ion can be selected from and this salt restored during calcining or decomposes any positively charged ion reverting to acid.Determine that the factor of suitability that concrete salt is used as electron-withdrawing anion source include, but are not limited to: salt expecting the shortage of the solubleness in solvent, positively charged ion adverse effect, ion pairing effect between positively charged ion and negatively charged ion, given the thermostability with negatively charged ion such as the hygroscopic nature of salt by positively charged ion.Cationic example suitable in the salt of electrophilic negatively charged ion includes but not limited to ammonium, trialkyl ammonium, tetra-allkylammonium, tetraalkyl , H +, [H (OEt 2) 2] +deng.
Further, the combination of one or more different electrophilic negatively charged ion of different ratios can be used, to adjust the concrete acidity of activator carrier to the level expected.Can make the combination of electrophilic component side by side or each ground and contact with oxide material with any order of the chemical treatment soild oxide acidity providing expectation.Such as, one side of the present disclosure adopts two or more electron-withdrawing anion source compounds in two or more independent contact procedures.
Therefore, the example of this method of the soild oxide of preparative chemistry process is as follows: the soild oxide of selection or the combination of soild oxide are contacted to form the first mixture with the first electron-withdrawing anion source compound; Calcine this first mixture and then contact to form the second mixture with the second electron-withdrawing anion source compound; Then the second mixture is calcined with the soild oxide of formation processing.In this approach, the first and second electron-withdrawing anion source compounds can be identical or different compounds.
According to another aspect of the present disclosure, chemically treated soild oxide comprises solid inorganic oxide material, the oxide material of mixing or the combination of inorganic oxide material, it uses the process of electrophilic component chemical, and optionally comprises metal-salt, metal ion or other metal-containing compound process by source metal.The non-limitative example of metal or metal ion comprises zinc, nickel, vanadium, titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium etc., or its combination.The example comprising the chemically treated soild oxide of metal or metal ion includes but not limited to the aluminum oxide of the impregnated zinc of chlorination, the aluminum oxide of the dipping titanium fluoridized, the aluminum oxide of the impregnated zinc of fluoridizing, the silica-alumina of the impregnated zinc of chlorination, the silica-alumina of the impregnated zinc of fluoridizing, the aluminum oxide of Sulfated impregnated zinc, the Zinc aluminate of chlorination, the Zinc aluminate of fluoridizing, Sulfated Zinc aluminate, with the aluminum oxide of the coating silica of hexafluorotitanic acid process, with zinc process and the aluminum oxide etc. of the coating silica then fluoridized, or its arbitrary combination.
Any method with metal impregnation solid oxide material can be used.Oxide compound and source metal, it is first-class that the method that typically salt or metal-containing compound contact can include, but are not limited to gelling, common gelling, a kind of compound is immersed in another kind.If expected, metal-containing compound is added in the form of a solution or is impregnated into soild oxide, and subsequently when the metal changing into load after calcining.So solid inorganic oxide can comprise further and is selected from following metal: zinc, titanium, nickel, vanadium, silver, copper, gallium, tin, tungsten, molybdenum etc., or the combination of these metals.Such as, zinc is generally used for steep solids oxide compound, because it can provide the catalyst activity of improvement with low cost.
Before soild oxide is by electrophilic anionic treatments, afterwards or simultaneously soild oxide available metal salt or metal-containing compound process.After any contact method, the typically mixture contacted of calcining solid compound, electrophilic negatively charged ion and metal ion.Alternatively, solid oxide material, electron-withdrawing anion source and metal-salt or metal-containing compound contact simultaneously and calcine.
Various method is for the formation of for chemically treated soild oxide of the present disclosure.Chemically treated soild oxide can comprise the product of contact of one or more soild oxides and one or more electron-withdrawing anion source.Soild oxide does not need to calcine before contacting with electron-withdrawing anion source.Product of contact is typically at soild oxide and electron-withdrawing anion source period of contact or calcine afterwards.Soild oxide can be calcining or not calcine.The various methods that preparation can be used for solid oxide activator carrier of the present disclosure are reported.Such as, this method is described in U.S. Patent number 6, and 107,230; 6,165,929; 6,294,494; 6,300,271; 6,316,553; 6,355,594; 6,376,415; 6,388,017; 6,391,816; 6,395,666; 6,524,987; 6,548,441; 6,548,442; 6,576,583; 6,613,712; 6,632,894; 6,667,274; 6,750,302; 7,226,886; 7,294,599; 7,601,655; With 7,732, in 542, its content is incorporated to herein with its entirety by reference.
According to one side of the present disclosure, by with electrophilic component, typically electron-withdrawing anion source contact, chemical treatment solid oxide material.Further, solid oxide material optionally with the process of metal ion chemistry, and is then calcined to form chemically treated soild oxide that is metallic or impregnating metal.According to another aspect of the present disclosure, solid oxide material and electron-withdrawing anion source contact simultaneously and calcine.
Oxide compound and electrophilic component, the typically salt of electrophilic negatively charged ion or the method for acid contact, can include, but are not limited to gelling, altogether gelling, a kind of compound is immersed in another kind of first-class.Therefore, after any contact method, the contact mixture of calcining solid oxide compound, electrophilic negatively charged ion and optional metal ion.
Solid oxide activator carrier (that is, chemically treated soild oxide) therefore can be produced by comprising following method:
1) soild oxide (or many kinds of solids oxide compound) is made to contact to form the first mixture with electron-withdrawing anion source compound (or multiple compounds); With
2) the first mixture is calcined to form solid oxide activator carrier.
According to another aspect of the present disclosure, solid oxide activator carrier (chemically treated soild oxide) is produced by comprising following method:
1) soild oxide (or many kinds of solids oxide compound) is made to contact to form the first mixture with the first electron-withdrawing anion source compound;
2) the first mixture that the first mixture produces calcining is calcined;
3) the first mixture of calcining is made to contact to form the second mixture with the second electron-withdrawing anion source compound; With
4) the second mixture is calcined to form solid oxide activator carrier.
According to still another aspect of the present disclosure, chemically treated soild oxide produces by making soild oxide contact with electron-withdrawing anion source compound or is formed, wherein solid oxide before contact electron-withdrawing anion source, period or calcine afterwards, and wherein substantially there is not aikyiaiurnirsoxan beta, organic boron or organoborate compound and Ionizing Ionic compound.
The soild oxide of calcination processing, usually under environment, typically under ridity environment, carries out the time of about 1 minute to about 100 hours at the temperature of about 200 DEG C to about 900 DEG C.Calcining the temperature of about 300 DEG C to about 800 DEG C, or alternatively, can be carried out at the temperature of about 400 DEG C to about 700 DEG C.Calcining can carry out about 30 minutes to about 50 hours, or about 1 is little of about 15 hours.Therefore, such as, calcining can carry out about 1 to about 10 hour at about 350 DEG C to about 550 DEG C temperature.Any suitable envrionment temperature can be adopted during calcining.Generally speaking, calcining is carried out in such as air in an oxidizing environment.Alternatively, inert atmosphere can be used, such as nitrogen or argon gas, or reducing atmosphere, such as hydrogen or carbon monoxide.
According to one side of the present disclosure, the source process of solid oxide material halogen ion, sulfate ion or negatively charged ion combination, optionally uses metal ion treatment, and then calcines the chemically treated soild oxide providing particulate solid form.Such as, solid oxide material can by sulfuric acid root (being called " sulfating agent "), chloride-ion source (being called " chlorizating agent "), fluoride sources (being called " fluorizating agent ") or its combined treatment, and calcining is to provide solid oxide activator.Useful acidic activated agent carrier includes but not limited to the aluminum oxide of bromination, the aluminum oxide of chlorination, the aluminum oxide fluoridized, Sulfated aluminum oxide, the silica-alumina of bromination, the silica-alumina of chlorination, the silica-alumina fluoridized, Sulfated silica-alumina, the silica-zirconium oxide of bromination, the silica-zirconium oxide of chlorination, the silica-zirconium oxide fluoridized, Sulfated silica-zirconium oxide, the silica-titania fluoridized, the aluminum oxide of hexafluorotitanic acid process, the aluminum oxide of the coating silica of hexafluorotitanic acid process, the silica-alumina of hexafluoro zirconate process, the silica-alumina of trifluoroacetic acid process, the boria-alumina fluoridized, the silicon-dioxide of Tetrafluoroboric acid process, the aluminum oxide of Tetrafluoroboric acid process, the aluminum oxide of phosphofluoric acid process, column clay, such as column montmorillonite, it optionally uses fluorochemical, muriate or vitriol process, the aluminum oxide of phosphorylation or other aluminate or phosphates, it optionally uses vitriol, fluorochemical or chloride treatment, or any combination above.Further, any one of these activator carriers optionally available metal ion processing.
Chemically treated soild oxide can comprise the soild oxide fluoridized of particulate solid form.The soild oxide fluoridized is formed by soild oxide and fluoriding agent.Fluorion, by forming the slurry of oxide compound in the ethanol of---because their volatility and low surface tensions---or water as included but not limited to the ethanol to three carbon in suitable solvent ratio, is added into oxide compound.The example of suitable fluorizating agent includes but not limited to hydrofluoric acid (HF), Neutral ammonium fluoride (NH 4f), ammonium bifluoride (NH 4hF 2), ammonium tetrafluoroborate (NH 4bF 4), ammonium silicofluoride (hexafluorosilicate) ((NH 4) 2siF 6), ammonium hexafluorophosphate (NH 4pF 6), hexafluorotitanic acid (H 2tiF 6), ammonium hexa-fluorotitanate ((NH 4) 2tiF 6), hexafluoro zirconate (H 2zrF 6), AlF 3, NH 4alF 4, its analogue, and its combination.Also trifluoromethanesulfonic acid and trifluoromethanesulfacid acid ammonium can be used.Such as, ammonium bifluoride (NH 4hF 2) can be used as fluorizating agent, due to its ease for use and operability.
If expected, soild oxide uses fluorizating agent process during calcining step.Any fluorizating agent of soild oxide fully can be contacted during calcining step can be used in.Such as, except those fluorizating agents described before, volatility organic fluoriding agents can be used.Example for the volatility organic fluoriding agents of this aspect of the disclosure includes but not limited to freonll-11, perflexane, perfluor benzene, methyl fuoride, trifluoroethanol etc. and its combination.Calcining temperature is usually sufficiently high with decomposition compound and release fluorine.If fluoridized while calcining, gaseous hydrogen fluoride (HF) or fluorine (F 2) itself also can use together with soild oxide.Also silicon tetrafluoride (SiF can be used 4) and comprise tetrafluoroborate (BF 4 -) compound.A kind of method easily of soild oxide and fluoriding agent that makes fluorizating agent is evaporated enter for making during calcining in the air-flow of solid oxidation Logistics.
Similarly, in another aspect of the present disclosure, chemically treated soild oxide comprises the soild oxide of the chlorination of particulate solid form.The soild oxide of chlorination is formed by making soild oxide and chlorinating agent.Chlorion is added into oxide compound by the slurry forming oxide compound in suitable solvent.Soild oxide can use chlorizating agent process during calcining step.Can use can be used as chlorine root origin and during calcining step any chlorizating agent of abundant catalytic oxidation thing, such as SiCl 4, SiMe 2cl 2, TiCl 4, BCl 3deng, comprise its mixture.Volatility organochlorine agent can be used.The example of suitable volatility organochlorine agent includes but not limited to some freonll-11, perna, methyl chloride, methylene dichloride, chloroform, tetracol phenixin, ethapon etc. or its arbitrary combination.Gaseous hydrogen chloride or chlorine itself also can use during calcining together with soild oxide.A kind of method easily of oxide compound and chlorinating agent is made to be chlorizating agent is evaporated enter for making during calcining in the air-flow of solid oxidation Logistics.
The fluorion existed before calcining solid oxide compound or the amount of chlorion are generally by weight about 1% to about 50%, and wherein weight percentage is based on the weight of soild oxide such as silica-alumina before calcining.According to another aspect of the present disclosure, the fluorion existed before calcining solid oxide compound or the amount of chlorion by weight about 1% to about 25%, and according to another aspect of the present disclosure, by weight about 2 to about 20%.According to of the present disclosure still on the other hand, the fluorion existed before calcining solid oxide compound or the amount of chlorion by weight about 4% to about 10%.Once with halogenide dipping, halided oxide can by the drying of any appropriate means, includes but not limited to that then air exhaust filtering evaporates, drying, spraying dry etc. under vacuum, but also may start the soild oxide of calcining step and moist dipping immediately.
Silica-alumina for the preparation of the silica-alumina of process typically has pore volume and is greater than about 0.5cc/g.According to one side of the present disclosure, pore volume is greater than about 0.8cc/g, and according to another aspect of the present disclosure, is greater than about 1.0cc/g.Further, silica-alumina usually has surface-area and is greater than about 100m 2/ g.According to another aspect of the present disclosure, surface-area is greater than about 250m 2/ g.Again, on the other hand, surface-area is greater than about 350m 2/ g.
The silica-alumina used in the disclosure typically has the alumina content of about 5% to about 95% by weight.According to one side of the present disclosure, the alumina content of silica-alumina is by weight about 5% to about 50%, or the aluminum oxide of about 8% to about 30%.On the other hand, the silica-alumina compound of high alumina content can be used, wherein the alumina content of these silica-alumina compound typically scope be by weight about 60% to about 90%, or the aluminum oxide of about 65% to about 80%.According to still another aspect of the present disclosure, solid oxide component comprises aluminum oxide and does not have silicon-dioxide, and according to another aspect of the present disclosure, solid oxide component comprises silicon-dioxide and do not have aluminum oxide.
Sulfated soild oxide comprises the solid oxide component of vitriol and particulate solid form, such as aluminum oxide or silica-alumina.Optionally, Sulfated oxide compound uses metal ion treatment further, thus the Sulfated oxide compound of calcining comprises metal.According to one side of the present disclosure, Sulfated soild oxide comprises vitriol and aluminum oxide.In certain situation, Sulfated aluminum oxide is formed by the method for wherein aluminum oxide sulfuric acid root such as sulfuric acid or vitriol such as ammonium sulfate process.The method is undertaken by the slurry forming aluminum oxide in the appropriate solvent such as ethanol or water that add the sulfating agent expecting concentration usually.Suitable organic solvent includes but not limited to the ethanol to three carbon, because their volatility and low surface tension.
According to one side of the present disclosure, the amount of the sulfate ion existed before being calcined is by weight about 0.5 to about 100 part of sulfate ion for about 100 parts of soild oxides by weight.According to another aspect of the present disclosure, the amount of the sulfate ion existed before being calcined is by weight about 1 to about 50 part of sulfate ion for about 100 parts of soild oxides by weight, with according to of the present disclosure still on the other hand, the sulfate ion of about 5 to about 30 parts is by weight for about 100 parts of soild oxides by weight.These weight ratios are based on the weight of soild oxide before calcining.Once with vitriol dipping, Sulfated oxide compound can be dry by any appropriate means, includes but not limited to that then air exhaust filtering evaporates, drying, spraying dry etc. under vacuum, but also may start calcining step immediately.
According to another aspect of the present disclosure, activator carrier for the preparation of disclosure catalyst composition comprise there is layering or non-hierarchical configuration can the activator carrier of ion-exchange, it includes but not limited to silicate and alumino-silicate compound or mineral, or its combination.In another aspect of the present disclosure, can ion-exchange layering aluminosilicate such as column clay be used as activator carrier.When acidic activated agent carrier comprise can the activator carrier of ion-exchange time, it is optionally with those process as disclosed herein of at least one electrophilic anion ratio, although typically can the activator carrier of ion-exchange without electrophilic anionic treatments.
According to another aspect of the present disclosure, activator carrier of the present disclosure comprises clay mineral, its layer having tradable positively charged ion and can expand.Typical clay mineral activator carrier includes but not limited to can the aluminosilicate such as column clay of layering of ion-exchange.Although use term " carrier ", and do not mean that and explain as the inert component of catalyst composition, but be interpreted as the active part of catalyst composition, because itself and metallocenes are closely related.
According to another aspect of the present disclosure, clay material of the present disclosure comprise with they state of nature or by the material of moistening, ion-exchange or the various ion processing of pillaredization.Typically, clay material activator carrier of the present disclosure comprises uses large positively charged ion, comprises the clay of the high charged metal complex cation ion-exchange of multinuclear.But clay material activator carrier of the present disclosure also comprises and includes but not limited to simple salt that the salt of Al (III), Fe (II), Fe (III) and Zn (II) and part such as halogen root, acetate, sulfate radical, nitrate radical or nitrite anions carries out the clay of ion-exchange.
According to another aspect of the present disclosure, activator carrier comprises column clay.Use term " column clay " refer to large, typically the high charged metal complex cation of multinuclear carry out the clay material of ion-exchange.The example of this ion includes but not limited to that electric charge can be the Keggin ion of such as 7+, various polyoxometallate and other heavy ions.Therefore, term pillaredization refers to simple permutoid reaction, and wherein the exchangeable cation of clay material is replaced by large, highly charged ion such as Keggin ion.These polycations are then fixed in the middle layer of clay and are changed into metal oxide " post " upon calcination, and effectively supporting clay seam is columnar structure.Therefore, once clay dried and calcining to produce the pillar stiffener between clay seam, the crystalline network of expansion is maintained and increases porosity.The shape and size in gained hole can be used as the pillared composite of use and the function change of parent clay material.Pillared and example that is column clay is shown in: T.J.Pinnavaia, Science 220 (4595), 365-371 (1983); J.M.Thomas, Intercalation Chemistry, (S.Whittington and A.Jacobson, eds.) the 3rd chapter, 55-99 page, Academic Press, Inc., (1972); U.S. Patent number 4,452,910; 5,376,611; With 4,060,480; Its content is incorporated to herein with its entirety by reference.
Pillared method uses the clay mineral of layer having exchangeable cation and can expand.Any column clay that can strengthen olefinic polymerization can be used in disclosure catalyst composition.So, include but not limited to malthacite for pillared suitable clay mineral; Terre verte, dioctahedron (Al) and trioctahedron (Mg) and its derivative, such as montmorillonite (wilkinite), nontronite, hectorite, or lithium algae soil (laponites); Halloysite; Vermiculite; Mica; Fluoronated mica; Chlorite; Mixed layer clay; Fibrous clay includes but not limited to sepiolite, attapulgite and polygorskite (palygorskites); Serpentine clay (serpentine clay); Illite; Lithium algae soil; Saponite; With its arbitrary combination.On the one hand, column clay activator carrier comprises wilkinite or montmorillonite.Bentonitic main ingredient is montmorillonite.
If need to anticipate column clay.Such as, column bentonite by under an inert atmosphere at about 300 DEG C drying carry out pre-treatment, typically under drying nitrogen, process about 3 hours, be then added into polymerization reactor.Although this document describes exemplary pre-treatment, be to be understood that and preheat and can carry out under other temperature and times many, comprise any combination of temperature and time step, they are all comprises in the disclosure.
Activator carrier for the preparation of disclosure catalyst composition can be combined with other inorganic carrier materials, includes but not limited to the inorganic oxide etc. of zeolite, inorganic oxide, phosphorylation.On the one hand, the typical solid support material of use includes but not limited to silicon-dioxide, silica-alumina, aluminum oxide, titanium oxide, zirconium white, magnesium oxide, boron oxide, Thorotrast, aluminate or phosphate, aluminum phosphate, silica-titania, the silicon-dioxide/titanium oxide of co-precipitation, its mixture or its arbitrary combination.
According to another aspect of the present disclosure, one or more metallocene compounds can with olefinic monomer and organo-aluminium compound pre-contact first time period, then make this mixture and activator carrier contact.Once the pre-contact mixture of metallocene compound (one or more), olefinic monomer and organo-aluminium compound and activator carrier contact, the composition comprising activator carrier is further called " afterwards contact " mixture.Rear contact mixture can allow to keep contacting the second segment time further, then loads the reactor by carrying out polymerization process wherein.
According to of the present disclosure still on the other hand, one or more metallocene compounds can with olefinic monomer and activator carrier pre-contact first time period, then make this mixture contact with organo-aluminium compound.Once metallocene compound (one or more), olefinic monomer contact with organo-aluminium compound with the pre-contact mixture of activator carrier, the composition comprising organoaluminum is further called " afterwards contact " mixture.Rear contact mixture can allow to keep contacting for the second time period further, then introduces polymerization reactor.
In one embodiment, activator or activator carrier are at catalyst system (namely, BIP) gross weight based on catalyzer in exists with following amounts: about 1wt.% to about 90wt.%, alternatively about 5wt.% to about 90wt.%, alternatively about 10wt.% to about 90wt.%.In one embodiment, metallocene compound (one or more) is from about 1:1 to about 1:1 with the weight ratio of activator carrier, 000,000.If used more than a kind of activator carrier, this ratio is based on the gross weight of activator carrier.In another embodiment, the scope of this weight ratio is from about 1:5 to about 1:100,000, or from about 1:10 to about 1:10,000.Again on the other hand, metallocene compound (one or more) is from about 1:20 to about 1:1000 with the weight ratio of activator carrier.
In one embodiment, openly the catalyst system of type comprises activator carrier (or activator) herein, and it comprises chemically treated soild oxide (such as, Sulfated aluminum oxide).The catalyst system comprising chemically treated soild oxide can as described hereinly when lacking any other activator work.In one embodiment, the catalyst system of type described herein comprises the chemically treated soild oxide as activator and does not contain other activator.In alternative embodiments, the catalyst system of type described herein comprises as the chemically treated soild oxide of activator and the other activator of at least one.
In one embodiment, other activator comprises aluminium alkoxide compound.As used herein, term " aikyiaiurnirsoxan beta " refers to aluminium alkoxide compound, composition, mixture or single kind (discrete species), and no matter how aikyiaiurnirsoxan beta is prepared, formed or otherwise provided.Aikyiaiurnirsoxan beta is also referred to as poly-(alkyl aluminum oxide) or Organoaluminoxy alkane.
Aluminium alkoxide compound of the present disclosure can be oligomeric aluminum compound, and it comprises linear structure, ring texture or cage structure, or the mixture of three.The disclosure considers the cyclic aluminoxane compounds with following formula:
Wherein R is the straight or branched alkyl with 1 to 10 carbon atom, and p is the integer of 3 to 20.Here the AlRO part shown also forms the repeating unit in wire aikyiaiurnirsoxan beta.Therefore, the disclosure also considers the wire aikyiaiurnirsoxan beta with following formula:
Wherein R is the straight or branched alkyl with 1 to 10 carbon atom, and q is the integer of 1 to 50.Further, be suitable for aikyiaiurnirsoxan beta of the present disclosure and can have formula R t 5r+ αr b r-αal 4ro 3rcage structure, wherein R tterminal linear or the branched-chain alkyl with 1 to 10 carbon atom; R bit is the bridging straight or branched alkyl with 1 to 10 carbon atom; R is 3 or 4; N is equaled with α al (3)-n o (2)+ n o (4), wherein n al (3)the quantity of three-fold coordination aluminium atom, n o (2)the quantity of two coordinating oxygen atoms, and n o (4)the quantity of 4 coordinating oxygen atoms.
In one embodiment, can be used as the aikyiaiurnirsoxan beta of the other activator in disclosure catalyst composition usually by formula such as (R-Al-O) p, R (R-Al-O) qalR 2deng expression.In these formulas, R group typically is straight or branched C 1-C 6alkyl, such as methyl, ethyl, propyl group, butyl, amyl group or hexyl.Methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta, isopropylaluminoxane, normal-butyl aikyiaiurnirsoxan beta, t-butyl-aluminoxane, sec-butylaluminoxane, isobutyl aluminium alkoxide, 1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane, isopentyl aikyiaiurnirsoxan beta, neo-pentyl aikyiaiurnirsoxan beta etc. or its arbitrary combination is included but not limited to according to the example of the spendable aluminium alkoxide compound of the disclosure.Methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide are prepared by trimethyl aluminium, triethyl aluminum or triisobutyl aluminium respectively, and are sometimes called poly-(methyl oxidation aluminium), poly-(ethyl aluminum oxide) and poly-(isobutyl-aluminum oxide).Use aikyiaiurnirsoxan beta also in the scope of the present disclosure in conjunction with trialkylaluminium, such as U.S. Patent number 4,794, disclosed in 096, be incorporated to herein with its entirety by reference.
The disclosure is considered respectively at aluminoxane formulas (R-Al-O) pwith R (R-Al-O) qalR 2many numerical value of middle p and q.In certain aspects, p and q is at least 3.But depend on how Organoaluminoxy alkane is prepared, stores and used, the numerical value of p and q can change in the single sample of aikyiaiurnirsoxan beta, and consider this combination of Organoaluminoxy alkane herein.
In preparation containing in the catalyst composition of aikyiaiurnirsoxan beta, total mole of the aluminium of aikyiaiurnirsoxan beta (or multiple aikyiaiurnirsoxan beta) with the mol ratio of transition metal complex in composition total mole usually at about 1:10 with about between 100,000:1; Alternatively, scope is from about 5:1 to about 15,000:1.Optionally, aikyiaiurnirsoxan beta can be added into the zone of convergency from about 0.01mg/L to about 1000mg/L, from about 0.1mg/L to about 100mg/L or from about 1mg/L to the scope of about 50mg/L.
In one embodiment, other activator comprises organoboron compound or organoborate compound.Organic boron or organoborate compound comprise neutral boron compounds, borate etc., or its combination.Such as, fluorine organoboron compound and fluorine organoborate compound is considered.
Any fluorine organic boron or fluorine organoborate compound can use together with the disclosure.The example that can be used for fluorine organoborate compound of the present disclosure includes but not limited to the aromatic yl acid salt fluoridized, such as DMA four (pentafluorophenyl group) borate, triphenylcarbenium four (pentafluorophenyl group) borate, four (pentafluorophenyl group) lithium tetraborate, DMA four [two (trifluoromethyl) phenyl of 3,5-] borate, triphenylcarbenium four [two (trifluoromethyl) phenyl of 3,5-] borate etc., or its mixture.The example of the fluorine organoboron compound that can use in the disclosure includes but not limited to three (pentafluorophenyl group) boron, three [two (trifluoromethyl) phenyl of 3,5-] boron etc., or its mixture.Although do not intend by following theory restriction, but think these examples of fluorine organic borate and fluorine organoboron compound and related compound when metallizing thing in conjunction with time form " weak coordination " negatively charged ion, as U.S. Patent number 5,919, disclosed in 983, its content is incorporated to herein with its entirety by reference.Applicant also considers to use in chemical structure two boron or two boron compound or other difunctional compounds that comprise two or more boron atom, such as J.Am.Chem.Soc., 2005,127, disclosed in pp.14756-14768, its content is incorporated to herein with its entirety by reference.
Generally speaking, any amount of organoboron compound can be used.According to one side of the present disclosure, organic boron or organoborate compound (or multiple compounds) total mole is from about 0.1:1 to about 15:1 with the molar ratio range of total mole of metallocene compound in catalyst composition (or multiple compounds).Typically, the fluorine organic boron of use or the amount of fluorine organoborate compound are the boron/borate compound of the transition metal complex compound about 0.5 mole to about 10 moles of every mole.According to another aspect of the present disclosure, the amount of fluorine organic boron or fluorine organoborate compound is the boron/borate compound of the transition metal complex about 0.8 mole to about 5 moles of every mole.
The catalyst system of preparation BIP can comprise promotor further.In one embodiment, promotor includes machine aluminium compound.This compound includes but not limited to the compound with following formula:
(R 1) 3Al;
Wherein R 1it is the aliphatic group with 2 to 10 carbon atoms.Such as, R 1can be ethyl, propyl group, butyl, hexyl or isobutyl-.
Other organo-aluminium compounds that can be used for catalyst composition disclosed herein can include but not limited to the compound with following formula:
Al(X 1) m(X 2) 3-m
Wherein X 1it is alkyl; X 2alkoxyl group or aryloxy, halogen root or hydride ion; And m is from 1 to 3, comprises 1 and 3.In one embodiment, X 1that there is 1 to about 20 carbon atom; The alkyl of 1 to 10 carbon atom alternatively.Be described previously the non-limitative example of this alkyl herein.In one embodiment, X 2alkoxyl group or aryloxy---its any one there is 1 to 20 carbon atom, halogen root or hydride ion.In one embodiment, X 2independently selected from fluorine or chlorine, alternatively, X 2chlorine.At formula Al (X 1) m(X 2) 3-min, m can be the numerical value of 1 to 3, comprises 1 and 3, and alternatively, m is 3.The value of M is not limited to integer; So this formula comprises sesquihalide compounds or other organoaluminum duster compound compounds.
The example being applicable to the organo-aluminium compound used according to the disclosure includes but not limited to trialkyl aluminium compound, dialkyl monohalide aluminum compound, aluminum dialkyl alkoxy compound, dialkylaluminum hydride compound, and its combination.The concrete non-limitative example of suitable organo-aluminium compound comprises trimethyl aluminium (TMA), triethyl aluminum (TEA), tri-n-n-propyl aluminum (TNPA), three n-butylaluminum (TNBA), triisobutyl aluminium (TIBA), tri-n-hexyl aluminum, tri-n-octylaluminium, diisobutylaluminium hydride, ethanol diethyl aluminum, diethylaluminum chloride etc., or its combination.
Generally speaking, the weight ratio of organo-aluminium compound and activator carrier is from about 10:1 to about 1:1000.If used more than a kind of organo-aluminium compound and/or more than a kind of activator carrier, this ratio is based on the gross weight of often kind of respective component.In another embodiment, the weight ratio of organo-aluminium compound and activator carrier is from about 3:1 to about 1:100, or from about 1:1 to about 1:50.
In one embodiment, prepare the catalyst system describing the BIP of type herein and comprise Cp*Cr (CH 3) 2(py) it includes machine aluminium compound with, Sulfated aluminum oxide activating agent carrier, optional activator---it comprises aikyiaiurnirsoxan beta and optional promotor---.In one embodiment, prepare the catalyst system describing type B IP herein and comprise Cp ' Cr (Cl) 2(THF); Sulfated aluminum oxide activating agent carrier, it includes machine aluminium compound with optional activator---it comprises aikyiaiurnirsoxan beta and optional promotor---.In one embodiment, prepare the catalyst system describing the BIP of type herein and comprise Cp " Cr (Cl) 2(THF) it includes machine aluminium compound with, Sulfated aluminum oxide activating agent carrier, optional activator---it comprises aikyiaiurnirsoxan beta and optional promotor---.
Catalyzer disclosed herein and catalyst system are intended to any olefine polymerizing process for all kinds polymerization reactor can be used to carry out.As used herein, " polymerization reactor " comprise can polymerization of olefin monomers to produce any polymerization reactor of homopolymer or multipolymer.This homopolymer and multipolymer are called resin or polymkeric substance.
Various types of reactor comprises those that can be described as batch, slurry, gas phase, solution, high pressure, tubulose or autoclave reactor.Gas-phase reactor can comprise fluidized-bed reactor or stagewise horizontal reactor.Slurry-phase reactor can comprise loop that is vertical or level.High-pressure reactor can comprise autoclave or tubular reactor.Type of reactor can comprise batch or successive processes.Successive processes can use interval or continuous print product withdraw.Method also can comprise the part or all of direct circulation of unreacted monomer, unreacted comonomer and/or thinner.
Polymerization reactor system of the present disclosure can comprise the reactor of a type in system or the multiple reactor of identical or different type.In multiple reactor, the generation of polymkeric substance can be included in by the several stages in interconnective at least two polymerization reactors be separated of transfer device, and this transfer device makes likely to be transferred in the second reactor by the polymkeric substance obtained from the first polymerization reactor.The polymeric reaction condition expected in one of reactor can be different from the operational condition of another reactor.Alternatively, the polymerization in multiple reactor can comprise polymkeric substance is transferred to following reaction device to carry out successive polymerization from reactor is manual.Multiple reactor system can comprise any combination, includes but not limited to the combination of the combination of multiple loop reactors, many Gas-phase reactor, annular-pipe reactor and Gas-phase reactor, many high-pressure reactors or high-pressure reactor and annular-pipe reactor and/or Gas-phase reactor.Multiple reactor can serial or parallel connection operation.
According to an aspect of the present disclosure, polymerization reactor system can comprise at least one loop slurry reactor, and it comprises endless tube that is vertical or level.Monomer, thinner, catalyzer and optionally any comonomer can continuously feeding to the annular-pipe reactor wherein occurring to be polymerized.Generally speaking, continuation method can comprise and monomer, catalyzer and thinner introduced polymerization reactor continuously and removes the suspension comprising polymer beads and thinner from this reactor continuously.Reactor effluent can be flashed to remove solid polymer from the liquid comprising thinner, monomer and/or comonomer.Various technology can be used for this separating step, includes but not limited to flash distillation, and it can comprise any combination of heating and decompression; Be separated by the Cyclonic action in cyclone separator or hydrocyclone; Or pass through centrifugation.
Typical slurry phase polymerisation process (also referred to as method for forming particles) is disclosed in such as, U.S. Patent number 3,248,179; 4,501,885; 5,565,175; 5,575,979; 6,239,235; 6,262,191; With 6,833, in 415, its each section is incorporated to herein with its entirety by reference.
The suitable thinner used in slurry polymerization includes but not limited to by the monomer that is polymerized and is the hydrocarbon of liquid at reaction conditions.The example of suitable thinner includes but not limited to hydrocarbon, such as propane, hexanaphthene, isopropyl alkane, normal butane, Skellysolve A, iso-pentane, neopentane and normal hexane.The reaction of some loop po lymerisation can occur under bulk conditions where no diluent is used.An example is the polymerization of propylene monomer, as U.S. Patent number 5, and 455, described in 314, it is incorporated to herein with its entirety by reference.
According to still another aspect of the present disclosure, polymerization reactor can comprise at least one Gas-phase reactor.This system can use the continuous print cycling stream comprising one or more monomers, and it is continuously circulated through fluidized-bed in the presence of a catalyst under polymerization conditions.Cycling stream can be withdrawn from and be circulated back to reactor from fluidized-bed.Meanwhile, polymer product can be withdrawn from from reactor and new or fresh monomer can be added to replace the monomer of polymerization.This Gas-phase reactor can comprise the process of the multistep vapour phase polymerization for alkene, wherein alkene is polymerized at least two independently vapour phase polymerization region with gas phase, makes polymer feed to the second zone of convergency containing catalyzer formed in first zone of convergency simultaneously.The Gas-phase reactor of one type is described in U.S. Patent number 5,352,749; 4,588,790; With 5,436, in 304, its each section is incorporated to herein with its entirety by reference.
According to still another aspect of the present disclosure, pressure polymerization reactor can comprise tubular reactor or autoclave reactor.Tubular reactor can have several regions of adding fresh monomer, initiator or catalyzer wherein.Monomer can be entrained in inert gas and in a region of reactor and introduce.Initiator, catalyzer and/or catalyst component can be carried secretly in the gas flow and introduce in another region of reactor.Air-flow can be mixed for polymerization mutually.Can suitably use heat and pressure to obtain best polymeric reaction condition.
According to still another aspect of the present disclosure, polymerization reactor can comprise solution polymerization reactor, wherein by suitable stirring or other modes, monomer is contacted with catalyst composition.The vehicle comprising inertia organic thinner or excess monomer can be used.If expected, when presence or absence liquid substance, monomer can be made to contact with catalytic reaction products with vapor phase.Under the zone of convergency remains on the temperature and pressure causing polymers soln formation in reaction medium.Can adopt to stir and control to obtain good temperature and keep uniform polyblend in the whole zone of convergency.Suitable mode is for dispersing the heat release of polymerization.
Be applicable to polymerization reactor of the present disclosure and can comprise the feed system of at least one raw material feed system, at least one catalyzer or catalyst component and/or any combination of at least one polymer recovery system further.For appropriate reactor system of the present disclosure can comprise further for feed purification, catalyst stores and preparation, extrude, reactor cooling, polymer recovery, fractionation, recovery, storage, filling, lab analysis and process control system.
In order to polymerization efficiency and the condition that provides resin properties and control comprise the concentration of temperature, pressure and various reactant.Polymerization temperature can affect catalyst productivity, polymericular weight and molecular weight distribution.Suitable polymerization temperature can be according to any temperature of Gibbs Free energy equation lower than de-polymerization temperature.Typically, depend on polymerization reactor type, this comprises such as from about 60 DEG C to about 280 DEG C with from about 70 DEG C to about 110 DEG C.
Suitable pressure also will change according to reactor and polymeric type.In annular-pipe reactor, the pressure of liquid polymerization is typically less than 1000 ft lbfs gauge pressure (psig) per square inch.The pressure of vapour phase polymerization usually about 200 to about 500psig.Tubulose or the polymerization of autoclave reactor mesohigh are carried out usually under about 20,000 to about 75,000psig.Polymerization reactor also can operate in the usual supercritical range occurred under comparatively high temps and pressure.More than Pressure/Temperature figure upper critical point, the operation of (supercritical phase) can provide advantage.
The concentration of various reactant can be controlled to produce the resin with some Physical and mechanical properties of polyoropylene.The end product of the proposal by resin formation and the method forming this product are determined resin properties.Mechanical properties comprises tension, flexibility, impact, creep, stress relaxation and hardness test.Physical properties comprises density, molecular weight, molecular weight distribution, temperature of fusion, second-order transition temperature, crystallization temperature of fusion, density, taxis, crack growth, long chain branching and rheology measurement.
The concentration of monomer, hydrogen, properties-correcting agent and electron donor is important in these resin properties of production.Hydrogen can be used for controlling molecular weight of product.Properties-correcting agent can be used for controlling product characteristics and influenced By Electron Donors tacticity.In addition, the concentration of poisonous substance is minimized, because poisonous substance impact reaction and product characteristics.In one embodiment, between polymerization period, hydrogen is added into reactor.Alternatively, between polymerization period, hydrogen is not added into reactor.
Polymkeric substance or resin can form various goods, include but not limited to bottle, drum, toy, household receptacle, utensil, film product, bucket, tanks, pipeline, mulch film and lining.Various method can be used for forming these goods, includes but not limited to blowing, extrusion molding, rotational molding, injection moulding, fiber sprinning, thermoforming, injection moulding etc.After polymerization, during manufacture and in order to end product expect character, additive and properties-correcting agent can be added into polymkeric substance to provide good process.Additive comprises surface-modifying agent such as surface slip agent, anti-caking agent (antiblocks), tackifier; Antioxidant is primary and secondary antioxidant such as; Pigment; Processing aid is wax/oil and fluoroelastomer such as; With specialist additive such as fire retardant, static inhibitor, scavenging agent, absorption agent, odor enhancers and degradation agents.
The catalyzer prepared according to the disclosure and catalyst system can be used for the polymerization of alkene such as alhpa olefin.In one embodiment, in the catalyzer of type described herein or catalyst system and reaction zone, alkene contacts to make olefinic polymerization under suitable reaction conditions (such as, temperature, pressure etc.).The straight or branched alhpa olefin with 2 to 30 carbon atoms can be used as olefin feedstock.The concrete example of alhpa olefin can comprise ethene, propylene, 1-butylene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene etc.This alhpa olefin can be used alone to produce homopolymer.In one embodiment, catalyst system as herein described for the production of polyethylene, such as, Natene or multipolymer.
After polymerization, additive and properties-correcting agent can be added into polymkeric substance with during manufacture and provide good process in order to the desirable properties of end product.Additive comprises surface-modifying agent such as surface slip agent, anti-caking agent, tackifier; Antioxidant is primary and secondary antioxidant such as; Pigment; Processing aid is wax/oil and fluoroelastomer such as; With specialist additive such as fire retardant, static inhibitor, scavenging agent, absorption agent, odor enhancers and degradation agents.
In one embodiment, when being used as polymerizing catalyst, the catalyst system of type described herein can show that catalyst activity scope is from about 10,000g (PE)/g (Cr)/h to about 5,000,000g (PE)/g (Cr)/h; Alternatively, from about 20,000g (PE)/g (Cr)/h to about 4,000,000; Alternatively, from about 30,000g (PE)/g (Cr)/h to about 3,000,000g (PE)/g (Cr)/h.With the poly grams of every gram of chrome catalysts production per hour (g (PE)/g Cr/h), catalyst activity is described.In one embodiment, catalyst activity does not rely on scope is from about 60 DEG C to about 120 DEG C; Alternatively from about 70 DEG C to about 115 DEG C; Alternatively from the temperature of reaction of about 80 DEG C to about 110 DEG C." do not rely on temperature of reaction " herein and refer to that catalyst activity change is less than about 20% in scope of disclosure, is less than about 15% alternatively; Be less than about 10% alternatively.
In one embodiment, the BIP of type described herein is unimodal resin.Herein, " mode " of fluoropolymer resin refers to the form of its molecular weight distribution curve, that is, as the outward appearance of the polymer weight fractin figure of the function of its molecular weight.Polymer weight fractin shows the weight fraction of dimensioning molecule.The polymkeric substance showing the molecular weight distribution curve at single peak can be described as unimodal polymerisation thing, and the polymkeric substance with the curve at display two different peaks can be described as bimodal polymers, and the polymkeric substance with the curve at display 3 different peaks can be described as three peak polymkeric substance, etc.Two or more peak can be described as multimodal.
In one embodiment, the weight-average molecular weight (M of BIP w) be about 10,000g/mol to about 2,500,000g/mol, alternatively about 50,000g/mol to about 2,000,000g/mol; Or alternatively about 100,000g/mol to about 1,500,000g/mol; Or alternatively, about 140,000g/mol to about 160,000g/mol and number-average molecular weight (M n) be about 3,000g/mol to about 150,000g/mol, alternatively, about 4,000g/mol to about 125,000g/mol, alternatively, about 5,000g/mol to about 100,000g/mol; Or alternatively, about 8,000g/mol to about 18,000g/mol.Weight-average molecular weight describes the molecular weight distribution of polymer composition and calculates according to equation 1:
M ‾ w = Σ i N i M i 2 Σ i N i M i - - - ( 1 )
Wherein Ni is the quantity of the molecule of molecular weight Mi.All molar mass average numbers are expressed as gram every mole (g/mol).Number-average molecular weight is by measuring the molecular weight of n polymer molecule, ask weight and, and the usual mean number of molecular weight of single polymkeric substance of calculating of being divided by by n.
M ‾ n = Σ i N i M i Σ i N i - - - ( 2 )
The molecular weight distribution (MWD) of BIP is weight-average molecular weight (M w) and number-average molecular weight (M n) ratio, it is also referred to as polydispersity index (PDI) or be called polymolecularity more simply.The feature of BIP composition can be wide molecular weight distribution (MWD).More specifically, it is about 2 to about 120 that BIP composition can have PDI, alternatively about 3 to about 100, alternatively about 4 to about 80.
The feature of BIP can be the degree of the branching existed in composition.Known short-chain branched (SCB) has impact to polymer property such as rigidity, Stretching Behavior, thermotolerance, hardness, impermeability, shrinkability, creep resistance, transparency, stress cracking resistance, flexibility, shock strength and semi-crystalline polymer such as poly solid state properties, and long chain branching (LCB) plays a role to polymer rheology.BIP composition can comprise and is equal to or less than often about 10,000 entire carbon atom about long chain branch (LCB) (about 1/10,000), alternatively, be equal to or less than often about 100,000 entire carbon atom about LCB (about 1/100,000), or alternatively, be equal to or less than often about 1,000,000 entire carbon atom about LCB (about 1/1,000,000).On the one hand, the LCB in BIP can use any appropriate means such as such as by increasing by peroxide treatment.On the one hand, treatments B IP makes LCB be increased to from being greater than about 0 to about 0.5, alternatively, from being greater than about 0 to about 0.25, alternatively, from being greater than about 0 to about 0.15, or alternatively, and from about 0.01 to about 0.08.
In one embodiment, the feature of the BIP of type described herein is that density is about 0.946g/ml to about 0.97g/ml, alternatively, about 0.948g/ml to about 0.968g/ml, alternatively, about 0.95g/ml to about 0.966g/ml, or alternatively, about 0.96g/ml to about 0.966g/ml, as measured by ASTM D1505.Such as, BIP can be density and is greater than about 0.945g/ml, alternatively, is greater than about 0.955g/ml, alternatively, is greater than the high density polyethylene(HDPE) of about 0.958g/ml.
In one embodiment, the melt index MI scope using the BIP of the Catalyst Production of type described herein to have is from about 0.01dg/min. to about 5.0dg/min., alternatively, from about 0.05dg/min. to about 4.0dg/min., alternatively, from about 0.1dg/min. to about 3.0dg/min, or alternatively, from about 0.8dg/min. to about 1.8dg/min.Melt index (MI) refers to the amount of polymers in the squeezing rheometer hole that can be forced through 0.0825 inch diameter when standing 2160 gram force in 10 minutes at 190 DEG C, as measured by ASTM D 1238.
In one embodiment, it is from about 0.1 to about 0.3 that the BIP of type described herein has Carreau Yasuda ' a ' parameter area, alternatively, and from about 0.5 to about 0.6, alternatively, from about 0.51 to about 0.59, alternatively, from about 0.54 to about 0.57.Carreau Yasuda ' a ' parameter (CY-a) is defined as rheology width parameter.Rheology width refers to the frequency dependence of transitional region between the newton of polymkeric substance and power law type shearing rate or polymer viscosity.Rheology width is the function of fluoropolymer resin relaxation time distribution, and relaxation time distribution is the function of resinous molecular structure or system structure.The curve calculation of CY-a parameter by hypothesis Cox-Merz rule acquisition and by producing in linear viscoelasticity dynamic oscillation frequency scan test with Carreau-Yasuda (CY) model-fitting of amendment, described Carreau-Yasuda (CY) model is represented by equation (3):
E = E o [ 1 + ( T ξ γ · ) a ] n - 1 a - - - ( 3 )
Wherein
E=viscosity (Pas)
A=rheology width parameter
Τ ξ=time of relaxation (one or more) [position in the time being described in transitional region]
Ε o=zero-shear viscosity (Pas) [definition newton platform]
N=power law constant [the final slope in definition high shear rate region].
For ease of model-fitting, power law constant n is remained steady state value.The meaning of CY model and derivative parameter and the details of explanation visible: C.A.Hieber and H.H.Chiang, Rheol.Acta, 28,321 (1989); C.A.Hieber and H.H.Chiang, Polym.Eng.Sci., 32,931 (1992); And R.B.Bird, R.C.Armstrong and O.Hasseger, Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, the second edition, John Wiley & Sons (1987), its each section is incorporated to herein with its entirety by reference.
In one embodiment, the BIP of type described herein has the zero-shear viscosity (Ε defined by equation (3) o) scope is from about 3.5 × 10 3pa-s is to about 7 × 10 4pa-s, alternatively from about 1 × 10 4pa-s is to about 6 × 10 4pa-s, alternatively from about 1.5 × 10 4pa-s is to about 6 × 10 4pa-s.Zero-shear viscosity refers to the viscosity of polymeric composition when shearing rate and indicates material molecule structure.Further, for polymer melt, the useful instruction of the melt strength of zero-shear viscosity normally in machining attribute such as blowing and foam technology and the bubble stability in film blowing.Such as, zero-shear viscosity is higher, melt strength or bubble stability better.
In one embodiment, it is from about 0.01s to about 0.10s that the BIP of type described herein has time of relaxation (τ) scope defined by equation (3), alternatively, from about 0.01s to about 0.03s, alternatively, from about 0.012s to about 0.08s, alternatively, from about 0.015s to about 0.05s.Relaxation rate refers to the viscosity time of relaxation of polymkeric substance and indicates the relaxation time distribution relevant to the wide distribution of molecular weight.
In one embodiment, the BIP of type described herein has the 100sec of the viscosity being defined as outlet pressure (head pressure) during instruction is extruded -1time shear viscosity (Ε 100) scope is from about 8 × 10 2pa-s is to about 6 × 10 4pa-s, alternatively, from about 8 × 10 2pa-s is to about 2 × 10 3pa-s, alternatively, from about 8 × 10 2pa-s is to about 1.2 × 10 3pa-s, alternatively, from about 8.5 × 10 2pa-s is to about 1.9 × 10 3pa-s, alternatively, from about 9 × 10 2pa-s is to about 1.8 × 10 3pa-s, or alternatively, from about 1 × 10 4pa-s is to about 6 × 10 4pa-s.This feature to during thin film fabrication to extrude easiness relevant, and be that the indirectly comparative of outlet pressure produced by polymkeric substance melt extrusion is in an extruder measured.Generally speaking, lower outlet pressure is beneficial to higher output speed, that is, the material extruding generation more pounds hourly.
Use that technology known in the art is such as extruded, blowing, injection moulding, fiber sprinning, thermoforming and casting, manufacture goods or terminal uses goods as the open fluoropolymer resin produced herein can be formed.Such as, fluoropolymer resin can be in flakes squeezed, is then thermoformed into terminal and uses goods, the such as assembly of container, cup, dish, pallet, toy or another product.In one embodiment, the fluoropolymer resin (such as, polyethylene) of production as described herein can form the film that can be used for food product pack.
In one embodiment, fluoropolymer resin of the present disclosure is made into film.Film of the present disclosure is by any appropriate means and produce under for the production of any felicity condition of film.In one embodiment, fluoropolymer resin forms film by cast-film process.In cast-film process, plastic melt by slit die be extruded cooling, on the roller of polishing to make film cooling.The speed control preliminary draft ratio of roller and film gauge (gauge).Film moves towards the second winding roller forward, completes cooling wherein.The film formed by fluoropolymer resin of the present disclosure (such as, polyethylene) can have any thickness that user expects.Alternatively, fluoropolymer resin of the present disclosure can film forming thickness be from about 0.3 mil (7 microns) to about 3 mils (76 microns), alternatively, from about 0.5 mil (12 microns) to about 2 mils (50 microns), alternatively, from about 0.8 mil (20 microns) to about 1.6 mils (40 microns).
Use the polymer resin of preparation as described herein can be beneficial to the film producing type described herein.Such as, the polymer resin (that is, BIP) of type described herein can show the machining feature of improvement when experiencing film manufacturing processes.In one embodiment, when comparing from the fluoropolymer resin of the similar melt index prepared with different catalyst systems, the fluoropolymer resin of type described herein can be extruded with similar extrusion pressure.This different catalyzer can be conventional catalyst system, such as metallocene (Ziegler Natta) catalyzer.
When comparing from the resin using different catalyst systems to produce, observation other in processing can be included in the manufacturing process with disclosure resin the similar outlet pressure and engine load that use.Outlet pressure refers to the blowdown pressure at forcing machine end herein, and engine load refers to forcing machine drawbar horsepower.
In one embodiment, BIP comprises Natene, and it forms the film shown and strengthen impermeability.Such as, described film can show the moisture vapour transmission rate (MVTR) of reduction.
In one embodiment, the MVTR scope that the blown film that the nominal 1.6-1.8mil produced by fluoropolymer resin of the present disclosure (that is, BIP) is thick has specification standardization is from about 0.30g. mil (g. mil/100in every 100 square inches of every days 2/ sky) to about 0.85g. mil/100in 2/ sky, alternatively, from about 0.3g. mil/100in 2/ sky is to about 0.6g. mil/100in 2/ sky, or alternatively, from about 0.3g. mil/100in 2/ sky is to about 0.5g. mil/100in 2/ sky, as measured according to ASTM F 1249.MVTR measures gaseous state H 2o is through barrier.MVTR also can be described as water vapor transmission rate (WVTR) (WVTR).Typically, MVTR measures in the special chamber by substrate/barrier material vertical separation.A chamber is dry atmosphere, and another chamber is humid atmosphere.Carry out test in 24 hours, under the condition of 5 kinds of any one combined can specifying temperature and humidity in " wetting " chamber, seen that how much humidity passes substrate/barrier to " doing " chamber from " wetting " chamber.
Embodiment
Generally describe theme, provide the following example as embodiment of the present disclosure and illustrate its practice and advantage.Should be appreciated that embodiment is provided by the mode of explanation and do not intend to limit the explanation limiting claim by any way.In the examples below that, MVTR is measured according to ASTM F-1249.Resin extruded become film after, use Mocon Permatran machine (W 3/31 type) test macro or similar machine to carry out the actual measurement of MVTR.Mocon instrument for measuring water permeate is developed by Modern Controls, Inc..Measure for completing MVTR, from random areas cutting 10 × 10cm sample of film.Sample to be then placed in sample test groove and to put into Mocon Permatran W3/31 unit.In this unit, testing film is exposed in the constant successive drying nitrogen gas stream of film side (discharge side) and the humidity-controlled nitrogen steady flow at opposite side (delivery side).Water vapour passes film from the humidified nitrogen side of test trough and enters the drying nitrogen side of test trough.In the change of the infrared energy absorption that the infrared light detecting systematic survey of the modulation of test trough discharge side is caused by the water vapour through film.By comparing the amplitude of the output signal obtained from the infrared light detecting system be arranged on test trough and the next self-contained amplitude had with reference to the signal of groove in the same instruments of the film of known rate of permeation, determine the rate of permeation of testing film.By convention, the numerical expression obtained from MVTR be the water passed in every 100 square inch of 24 hours of each mil (one-thousandth of an inch) thickness grams (or, in metric system, the grams of the water that every mm of thickness every square metre is passed in 24 hours).
Embodiment 1
Preparation comprises the catalyst system describing type herein of semi-sandwich chromium transition metal complex, Sulfated alumina supporter and optional TIBA promotor.All operate in the nitrogen atmosphere of purifying under use the Xi Laike technology of standard (Schlenk line) or glove box techniques to carry out.From potassium solvent distillation THF, and anhydrous diethyl ether, heptane, pyridine and toluene (Fisher Scientific Company) are stored on the aluminum oxide of activation.To all solvent degas and storage under a nitrogen.Chromium trichloride (III) and all organic ligands are bought from Aldrich Chemical Company.Li (η 5-C 5h 4cH 2cH 2cH=CH 2) prepared by the method described in the J.Org.Chem.36 such as Brieger (1971) p243, and Li (η 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2) prepare according to the method for the uses in J.Organmet.Chem.592 (1999) such as Bochmann.Complex compound (I), Cp*Cr (CH 3) 2(py) the method preparation, by describing in the J.Am.Chem.Soc.111 such as Theopold (1989) p9127.
For Cp ' Cr (Cl) 2(THF) (Cp '=η 5-C 5h 4cH 2cH 2cH=CH 2) complex compound (II) by being included in the Li (η adding 1 equivalent in THF at 0 DEG C 5-C 5h 4cH 2cH 2cH=CH 2) (0.5 gram, 4.0mmol) to CrCl 3the method preparation of the THF solution of 3THF (1.5 grams, 4.0mmol).Mixture is at room temperature stirred 5 hours.Remove under vacuo after THF, obtain in the admixture solvent of toluene and heptane at-35 DEG C blue crystallization (0.3 gram, productive rate: 31%)." the Cr (Cl) for Cp 2(THF) (Cp "=η 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2) complex compound (III) by being included in the Li (η adding 1 equivalent in THF at 0 DEG C 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2) (0.678 gram, 4.0mmol) to CrCl 3the method preparation of the THF solution of 3THF (1.5 grams, 4.0mmol).Mixture is at room temperature stirred 5 hours.Remove under vacuo after THF, at-35 DEG C heptane mixed solvent in obtain blue crystallization (0.32 gram, productive rate: 28%).
Use the aluminum oxide A from W.R.Grace Company, be incipient wetness with ammonium sulfate solution dipping, prepare Sulfated solid oxide activator carrier (SSA).Typically, the surface-area of this aluminum oxide is about 330m 2/ gram and pore volume be about 1.3cc/ gram.The amount of the ammonium sulfate used equals 20% of initial oxidation aluminium.Volume of water for dissolving ammonium sulfate (namely every gram pending the non-2.6mL water of aluminum oxide) is calculated from the total pore volume of initial sample.Therefore, the solution of every ml water about 0.08 gram of ammonium sulfate is used.Sand shape thing dried overnight at vacuum oven 120 DEG C that gained is moistening, and 35 eye mesh screens that then sieve.Finally, material is activated 6 hours at 550 DEG C in the fluidization flow of dry air.Then storage of samples under a nitrogen.
Comprise complex compound (I), (II) or (III), SSA and promotor catalyst system be used for the polymerization of ethene.Generally speaking, all being aggregated in one gallon of (3.785 liters) stainless steel autoclave reactor is carried out, and comprises two liters of isopropyl alkane as thinner and the hydrogen that adds from 325cc additional reservoir in reactor.The Δ P of hydrogen refers to the pressure drop from 600psig original pressure in this container.The half sandwich solution (1mg/mL) based on chromium is prepared in the usual toluene by the catalyst precursor of 20mg being dissolved in 20ml.In whole operation, reactor is made to remain on the service temperature of expectation by Automatic-heating-cooling system.
Polymerization process can use one of two kinds of conventional schemes to carry out.Operational version 1, under isopropyl alkane purges, loads TIBA solution (in heptane 25%) in cold reactor, follows the mixture in toluene by semi-sandwich chromium complex compound and sulfation SSA.Closed reactor and add the isopropyl alkane of 2 liters.Open ethylene feed, feeding ethylene as requested, to keep reactor pressure within 5 degree that reactor are heated to rapidly service temperature.Then during polymerization process, hydrogen is introduced reactor.For copolymerization, 1-hexene is put into together with initial ethylene feed.At the end of one hour, light (flare) reactor content; Use nitrogen purging reactor, then open.By polymer powder dried overnight under vacuo at 60 DEG C.Operational version II, under isopropyl alkane purges, the mixture of TIBA solution (in heptane 25%) and SSA is loaded cold reactor, is then the semi-sandwich chromium compound in toluene.Closed reactor and add 2 liters of isopropyl alkane.Open ethylene feed, feeding ethylene as requested, to keep reactor pressure within 5 degree that reactor are heated to rapidly service temperature.Then, during polymerization process, hydrogen is introduced reactor.For copolymerization, 1-hexene is put into together with initial ethylene feed.At the end of one hour, light reactor content; Use nitrogen purging reactor, and then open.By polymer powder dried overnight under vacuo at 60 DEG C.
For the sample using complex compound (I) and sulfation SSA activation support preparation, polymerization process comprises makes the TIBA of 0.2mL mix under a nitrogen in Glass tubing with the sulfation SSA of 0.15 gram.After about 1 minute, being less than at 40 DEG C, slurry is added into reactor.0.001 gram of Cp*Cr (CH in 1mL toluene 3) 2(py) also reactor is added into.Sealed reactor and add 2L isopropyl alkane and start under 700rpm stir.Along with temperature of reactor is close to 100 DEG C, starts to add H2 (366psi) and ethene (555psi) and obtain rapidly the setting point of 105 DEG C.At reactor being remained on 105 DEG C 60 minutes and then by evaporative emissions to flare system.Polyethylene solids stays in the reactor by the method.It produces the polyethylene (active, 1,262,069g (PE)/g (Cr)/h) of 221.4 grams.
For the sample using complex compound (II) and sulfation SSA to activate support preparation, polymerization process comprises the TIBA adding 0.2mL respectively at 40 DEG C, the sulfation SSA of 0.3 gram and 0.002 gram of Cp ' Cr (Cl) in 1mL toluene 2(THF) (Cp '=η 5-C 5h 4cH 2cH 2cH=CH 2) to reactor.Sealed reactor and add 2L isopropyl alkane and start under 700rpm stir.Along with temperature of reactor is close to 75 DEG C, start to add ethene (550psi) and the setting point of acquisition 80 DEG C rapidly.At reactor being remained on 80 DEG C 60 minutes and then by evaporative emissions to flare system.Polyethylene solids stays in the reactor by the method.It produces the polyethylene (active, 1,083,455g (PE)/g (Cr)/h) of 358.6 grams.
For the sample using complex compound (III) and sulfation SSA to activate support preparation, polymerization process comprises the TIBA adding 0.2mL respectively at 40 DEG C, 0.3 gram of sulfation SSA and the 0.002 gram of Cp " Cr (Cl) in 1mL toluene 2(THF) (Cp "=η 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2) to reactor.Sealed reactor and add 2L isopropyl alkane and start under 700rpm stir.Along with temperature of reactor is close to 85 DEG C, start to add ethene (402psi) and the setting point of acquisition 90 DEG C rapidly.At reactor being remained on 90 DEG C 60 minutes and then by evaporative emissions to flare system.Polyethylene solids stays in the reactor by the method.It produces the polyethylene (active, 366,163g (PE)/g (Cr)/h) of 108.1 grams.
Prepare 48 samples and the condition, component and the group component that use in each sample and catalyst activity altogether to sum up in Table 1.
Table 1
Then other sign is carried out to polymer samples.According to ASTM D1238 condition F at 190 DEG C with 2,160 gram weight measure melt index (MI, g/10min).According to ASTM D1238 condition E at 190 DEG C with 21,600 gram weight measure high load melt index (HLMI, g/10min).According to ASTM D1505 and ASTM D1928, method C, in compression moulded samples---cool with about 15 DEG C per hour and at room temperature regulate about 40 hours, measuring density polymer with gram every cubic centimetre (g/cc).Use PL 220SEC high temperature chromatographic unit (Polymer Laboratories), with trichlorobenzene (TCB) for solvent, flow velocity is 1mL/ minute, at the temperature of 145 DEG C, obtains molecular weight and molecualr weight distribution.With the BHT of 0.5g/L concentration (2,6 di tert butyl 4 methyl phenol) as the stablizer in TCB.For the nominal polymer concentration of 1.5mg/mL, use the volume injected of 200 μ L.By heating 5 hours at 150 DEG C, stirring gently once in a while, carrying out the dissolving of sample in stable TCB.The post used is 3 PLgel Mixed A LS post (7.8 × 300mm) and with wide linear polyethylene standard (the Chevron Phillips measuring molecular weight bHB 5003) calibration.These results characterized are summed up in table 2.
Table 2
The MWD sample using different catalysts system disclosed herein to prepare presents in FIG, and Fig. 2 provides the turning radius as the figure of the function of MW.
Embodiment 2
Obtain the resin and the film performance testing them that use the generation of the catalyst system of type described herein.Particularly, preparation comprises poly two groups of BIP samples and is called sample 49-52.Sample 49 and 50 is prepared as first group of BIP sample and sample 51 and 52 is the second group of BIP sample prepared after a while.Different catalyst system preparations is used to comprise the sample 53-59 of polyvinyl resin.Particularly, sample 53 uses the commercial resin prepared of Ziegler-Natta catalyst and melt index is 1; Sample 54 is the commercial resin that uses conventional chrome catalysts system to prepare and melt index is 1; Sample 55 is the commercial unimodal resin that uses ziegler natta catalyst system to prepare and melt index is 2; Sample 56 and 57 is the commercial resin that uses the chrome catalysts system of modification to prepare and melt index is respectively 2 and 1; Sample 58 is multi-modal resin, and MI is 2.81 and comprises high molecular (HMW) component of lower molecular weight (LMW) component of the MW=26kg/mol of 60% and the MW=220kg/mol of 40%; And sample 59 is multi-modal resin, MI is 1.2 and comprises the HMW component of the LMW component of the MW=20kg/mol of 40% and the MW=220kg/mol of 60%, and it has used peroxide treatment to produce 0.05LCB/10, the LCB value of 000 carbon atom.GPC carries out on sample 49-52 and the figure of these results describes in figures 3 and 4.Result shows, openly the BIP embodiment for unimodal composition of type has wide MWD herein.The other result of the gpc analysis of 11 samples of test presents in table 3.
Table 3
Sample number M n M w M z M w/M n M z/M w
kg/mol kg/mol kg/mol kg/mol
49 13 148 1357 11.4 9.2
50 15 154 1346 10.1 8.7
51 14 148 1482 10.7 10.0
52 11 154 1680 13.6 10.9
53 22 140 704 6.2 5.0
54 18 144 1083 8.0 7.5
55 18 115 437 6.3 3.8
56 15 135 1439 8.8 10.6
57 16 153 1470 9.5 9.6
58 15 107 345 7.2 3.2
59 11 114 294 10.0 2.6
Result show sample 49 to 52 have obtain with business chrome catalysts (sample 54,56 and 58) those within the scope of molecular weight distribution, mean and extrude the similar of easiness and these commerical prods.
Also the rheological behavior of sample 49-59 is assessed and those results present in table 4.
Table 4
(namely result shows the BIP embodiment of type described herein, sample 49-52) relative to those typical bimodal resin such as sample 58 and 59, there is higher zero-shear viscosity and viscosity (Eta100) is extruded in too much impact, represent better film bubble of blown film and do not affect output speed.
Also the impermeability of sample is assessed and these results present in table 5.
Table 5
Result shows, homopolymer sample 51 and 52 obtains minimum MVTR quantity for similar film specification with the typical melt index of commercial applications.Further, MVTR, as the figure of the function of zero-shear viscosity, Fig. 5, represents that sample keeps MVTR advantage by having the film bubble of blown film stability similar with some commercial resins simultaneously.
Although show and describe embodiments of the present invention, those skilled in the art can modify it and not deviate from spirit of the present invention and instruction.Embodiment as herein described is only exemplary, does not intend to be restrictive.Many changes of open invention herein and amendment are possible and within the scope of the invention.Clearly stating the situation of numerical range or limit value, this expression scope or limit value should be understood to comprise drop on this clear statement scope or limit value in the iteration ranges of same degree or limit value (such as, from about 1 to about 10 comprises 2,3,4 etc.; Be greater than 0.10 and comprise 0.11,0.12,0.13 etc.).Such as, when whenever openly there is lower limit R lwith upper limit R unumerical range, specifically disclose any numerical value dropped within the scope of this.Specifically, the numerical value dropped in following scope is specifically disclosed: R=R l+ k* (R u-R l), wherein k is 1% to 100% variable increased progressively with 1%, that is, k be 1%, 2%, 3%, 4%, 5% ..., 51% .50%, 52% ... ..95%, 96%, 97%, 98%, 99% or 100%.And, also specifically disclose by the above-mentioned any numerical range limiting two R numerical definitenesses.With regard to any key element of claim, the use of term " optionally " is intended to represent that described key element is necessary, or dispensable alternatively.Two kinds of selections are all intended within the scope of the claims.Wider term such as comprises, comprise, the use to have etc. should be understood to narrower term such as by ... composition, substantially by ... composition, substantially by ... formation etc. provides support.
Therefore, protection domain is not limited to the description of explaining above, but is only limited by claim, and this scope comprises all Equivalents of claim theme.Each and all claims are incorporated to specification sheets as embodiments of the present invention.Therefore, claim is the other embodiment of further instruction and the present invention.Discussion herein is not to recognize that it is prior art of the present invention, especially may have any reference of the publication date after the application's priority date.The disclosure of all patents quoted herein, patent application and publication is incorporated to herein by reference, and degree is that they provide exemplary, procedural to those contents explained herein or other details are supplemented.

Claims (17)

1. catalyst system, it comprises semi-sandwich chromium complex compound, activator carrier and optional promotor, and wherein said semi-sandwich chromium complex compound is characterised in that general formula:
M(Z)(R 1)(R 2)(L n)
Wherein M is chromium; Z comprises η 5-C 5h 4cH 2cH 2cH=CH 2or η 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2; R 1and R 2be halogen root or alkyl independently; L ncomprise neutral electron donor group; With n=0,1 or 2.
2. catalyst system according to claim 1, wherein L ntetrahydrofuran (THF) (THF), acetonitrile, pyridine, ether or dipyridyl.
3. catalyst system according to claim 1, wherein said semi-sandwich chromium complex compound comprises η 5-C 5h 4cH 2cH 2cH=CH 2cr (Cl) 2or η (THF) 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2cr (Cl) 2(THF).
4. catalyst system according to claim 1, wherein said activator carrier comprises chemically treated inoganic solids oxide compound.
5. catalyst system according to claim 4, wherein said chemically treated inoganic solids oxide compound comprises the aluminum oxide of bromination, the aluminum oxide of chlorination, the aluminum oxide fluoridized, Sulfated aluminum oxide, the silica-alumina of bromination, the silica-alumina of chlorination, the silica-alumina fluoridized, Sulfated silica-alumina, the silica-zirconium oxide of bromination, the silica-zirconium oxide of chlorination, the silica-zirconium oxide fluoridized, Sulfated silica-zirconium oxide, column clay, aluminate or phosphate or its any combination.
6. catalyst system according to claim 4, wherein said inoganic solids oxide compound comprises silica-alumina, and alumina content is by weight 5% to 95%.
7. catalyst system according to claim 1, wherein said activator carrier comprises Sulfated aluminum oxide.
8. catalyst system according to claim 1, comprises aikyiaiurnirsoxan beta, organoboron compound or its combination further.
9. catalyst system according to claim 8, wherein said organoboron compound is organoborate compound.
10. catalyst system according to claim 1, wherein said promotor includes machine aluminium compound.
11. catalyst systems according to claim 10, wherein said organo-aluminium compound has general formula:
(R 1) 3Al
Wherein R 1it is the aliphatic group with 2 to 10 carbon atoms.
12. catalyst systems according to claim 1, the scope of its catalyst activity is 10,000g (PE)/g Cr/h to 5,000,000g (PE)/g Cr/h.
13. catalyst systems according to claim 1, its catalyst activity does not rely on scope from the temperature of reaction of 70 DEG C to 105 DEG C.
14. formula Cp ' Cr (Cl) 2(L n) compound, wherein Cp ' is η 5-C 5h 4cH 2cH 2cH=CH 2and L npyridine, THF or ether.
15. formula Cp " Cr (Cl) 2(L n) compound, wherein Cp " is η 5-C 5h 4c (Me) 2cH 2cH 2cH=CH 2and L npyridine, THF or ether.
16. catalyst systems, it comprises compound according to claim 14, activator carrier and optional promotor.
17. catalyst systems, it comprises compound according to claim 15, activator carrier and optional promotor.
CN201180045712.XA 2010-09-24 2011-09-20 Catalyst system improves impervious fluoropolymer resin with having Active CN103154048B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US12/890,455 US8501651B2 (en) 2010-09-24 2010-09-24 Catalyst systems and polymer resins having improved barrier properties
US12/890,455 2010-09-24
PCT/US2011/052266 WO2012040147A1 (en) 2010-09-24 2011-09-20 Novel catalyst systems and polymer resins having improved barrier properties

Publications (2)

Publication Number Publication Date
CN103154048A CN103154048A (en) 2013-06-12
CN103154048B true CN103154048B (en) 2015-07-29

Family

ID=44759778

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180045712.XA Active CN103154048B (en) 2010-09-24 2011-09-20 Catalyst system improves impervious fluoropolymer resin with having

Country Status (8)

Country Link
US (2) US8501651B2 (en)
EP (1) EP2619235B1 (en)
CN (1) CN103154048B (en)
BR (1) BR112013006892B1 (en)
CA (2) CA2996547C (en)
ES (1) ES2677068T3 (en)
WO (1) WO2012040147A1 (en)
ZA (1) ZA201302163B (en)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8828529B2 (en) 2010-09-24 2014-09-09 Chevron Phillips Chemical Company Lp Catalyst systems and polymer resins having improved barrier properties
US8501651B2 (en) 2010-09-24 2013-08-06 Chevron Phillips Chemical Company Lp Catalyst systems and polymer resins having improved barrier properties
US9018329B2 (en) * 2011-09-02 2015-04-28 Chevron Phillips Chemical Company Lp Polymer compositions having improved barrier properties
US9284391B2 (en) 2011-09-02 2016-03-15 Chevron Phillips Chemical Company Lp Polymer compositions having improved barrier properties
US8895679B2 (en) 2012-10-25 2014-11-25 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US8937139B2 (en) 2012-10-25 2015-01-20 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US9034991B2 (en) 2013-01-29 2015-05-19 Chevron Phillips Chemical Company Lp Polymer compositions and methods of making and using same
US8877672B2 (en) 2013-01-29 2014-11-04 Chevron Phillips Chemical Company Lp Catalyst compositions and methods of making and using same
US9156970B2 (en) 2013-09-05 2015-10-13 Chevron Phillips Chemical Company Lp Higher density polyolefins with improved stress crack resistance
US10246528B2 (en) 2014-01-09 2019-04-02 Chevron Phillips Chemical Company Lp Chromium (III) catalyst systems with activator-supports
US9163098B2 (en) 2014-01-10 2015-10-20 Chevron Phillips Chemical Company Lp Processes for preparing metallocene-based catalyst systems
US9422382B2 (en) 2014-06-13 2016-08-23 Exxonmobil Chemical Patents Inc. Multiple catalyst system and polymerization process for use thereof
US10329363B2 (en) 2015-03-23 2019-06-25 Exxonmobil Chemical Patents Inc. Group 6 transition metal catalyst compound and use thereof
CN107889472B (en) 2015-05-11 2021-09-07 格雷斯公司 Process for preparing modified clay supported metallocene polymerization catalysts, the catalysts prepared and their use
BR112017024300A2 (en) 2015-05-11 2018-07-24 Grace W R & Co process for the production of modified clay, produced modified clay and its use
US9289748B1 (en) 2015-06-11 2016-03-22 Chevron Phillips Chemical Company Lp Treater regeneration
US9861955B2 (en) 2015-06-11 2018-01-09 Chevron Phillips Chemical Company, Lp Treater regeneration
CN108137729B (en) 2015-10-22 2021-02-05 埃克森美孚化学专利公司 Catalysts for forming multimodal polymers
GB201717185D0 (en) 2016-10-19 2017-12-06 Bhargava Saumitra Compression blow formed hdpe containers and methods of making the same
CN110621388B (en) 2017-05-03 2021-10-29 切弗朗菲利浦化学公司 Regenerating desiccant in an off-line processor of a polyolefin production process
US10792609B2 (en) 2018-05-07 2020-10-06 Chevron Phillips Chemical Company Lp Nitrogen conservation in polymerization processes
US11377541B2 (en) * 2019-07-26 2022-07-05 Chevron Phillips Chemical Company Lp Blow molding polymers with improved cycle time, processability, and surface quality

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5418200A (en) * 1991-03-29 1995-05-23 Chevron Chemical Company Cyclopentadienyl group 6B metal α-olefin polymerization catalysts and process for polymerizing α-olefins
EP0620830B1 (en) * 1992-11-06 1997-04-23 Chevron Chemical Company ALPHA-OLEFIN POLYMERIZATION CATALYSTS COMPRISING SUPPORTED CYCLOPENTADIENYL GROUP 6b METAL OXO, THIO, IMIDO AND PHOSPHIDO COMPOUNDS AND PROCESS FOR POLYMERIZING ALPHA-OLEFINS
CN1989158A (en) * 2004-06-25 2007-06-27 切弗朗菲利浦化学公司 Polymerization catalysts for producing polymers with low levels of long chain branching

Family Cites Families (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3248179A (en) 1962-02-26 1966-04-26 Phillips Petroleum Co Method and apparatus for the production of solid polymers of olefins
US4060480A (en) 1971-09-03 1977-11-29 Chevron Research Company Hydrocarbon hydroconversion process employing hydroxy-aluminum stabilized catalysts supports
US4501885A (en) 1981-10-14 1985-02-26 Phillips Petroleum Company Diluent and inert gas recovery from a polymerization process
US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
US4452910A (en) 1982-06-15 1984-06-05 Standard Oil Company (Indiana) Chromium expanded smectite clay
US4794096A (en) 1987-04-03 1988-12-27 Fina Technology, Inc. Hafnium metallocene catalyst for the polymerization of olefins
US5565175A (en) 1990-10-01 1996-10-15 Phillips Petroleum Company Apparatus and method for producing ethylene polymer
US5575979A (en) 1991-03-04 1996-11-19 Phillips Petroleum Company Process and apparatus for separating diluents from solid polymers utilizing a two-stage flash and a cyclone separator
DE69219668T2 (en) 1991-03-29 1997-09-11 Chevron Usa Inc Alpha-olefin polymerization catalysts containing cyclopentadienyl group based on a metal of the 6B group and process for the polymerization of alpha-olefins
AU650787B2 (en) 1991-12-09 1994-06-30 Phillips Petroleum Company Process for preparing a pillared chain silicate clay
US5436304A (en) 1992-03-19 1995-07-25 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
US5352749A (en) 1992-03-19 1994-10-04 Exxon Chemical Patents, Inc. Process for polymerizing monomers in fluidized beds
US5455314A (en) 1994-07-27 1995-10-03 Phillips Petroleum Company Method for controlling removal of polymerization reaction effluent
WO1996023006A1 (en) 1995-01-26 1996-08-01 Chevron Chemical Company Cyclopentadienyl group 6b metal-alkali metal alpha-olefin polymerization catalysts and their use in polymerization processes
US5593931A (en) 1995-03-03 1997-01-14 Chevron Chemical Company Cyclopentadienyl group 6b metal alpha-olefin polymerization catalysts and process for polymerizing alpha-olefins
RU2178422C2 (en) 1996-03-27 2002-01-20 Дзе Дау Кемикал Компани Olefin polymerization catalyst activator, catalytic system, and polymerization process
US6432496B1 (en) 1997-06-06 2002-08-13 Eastman Chemical Company High density polyethylene films with improved barrier properties
US7176259B1 (en) 1997-06-06 2007-02-13 Eastman Chemical Resins, Inc. High density polyethylene films with improved barrier properties
US6239235B1 (en) 1997-07-15 2001-05-29 Phillips Petroleum Company High solids slurry polymerization
US5942462A (en) 1997-10-20 1999-08-24 Akzo Nobel N.V. Process for preparing group 6 metal-based olefin polymerization catalyst component
KR100531628B1 (en) 1998-03-20 2005-11-29 엑손모빌 케미칼 패턴츠 인코포레이티드 Continuous slurry polymerization volatile removal
US6300271B1 (en) 1998-05-18 2001-10-09 Phillips Petroleum Company Compositions that can produce polymers
US6165929A (en) 1998-05-18 2000-12-26 Phillips Petroleum Company Compositions that can produce polymers
US6107230A (en) 1998-05-18 2000-08-22 Phillips Petroleum Company Compositions that can produce polymers
US6294494B1 (en) 1998-12-18 2001-09-25 Phillips Petroleum Company Olefin polymerization processes and products thereof
US6262191B1 (en) 1999-03-09 2001-07-17 Phillips Petroleum Company Diluent slip stream to give catalyst wetting agent
US6355594B1 (en) 1999-09-27 2002-03-12 Phillips Petroleum Company Organometal catalyst compositions
US6376415B1 (en) 1999-09-28 2002-04-23 Phillips Petroleum Company Organometal catalyst compositions
US6395666B1 (en) 1999-09-29 2002-05-28 Phillips Petroleum Company Organometal catalyst compositions
US6548441B1 (en) 1999-10-27 2003-04-15 Phillips Petroleum Company Organometal catalyst compositions
US6391816B1 (en) 1999-10-27 2002-05-21 Phillips Petroleum Organometal compound catalyst
US6613712B1 (en) 1999-11-24 2003-09-02 Phillips Petroleum Company Organometal catalyst compositions with solid oxide supports treated with fluorine and boron
US6548442B1 (en) 1999-12-03 2003-04-15 Phillips Petroleum Company Organometal compound catalyst
US6750302B1 (en) 1999-12-16 2004-06-15 Phillips Petroleum Company Organometal catalyst compositions
US6524987B1 (en) 1999-12-22 2003-02-25 Phillips Petroleum Company Organometal catalyst compositions
US6632894B1 (en) 1999-12-30 2003-10-14 Phillips Petroleum Company Organometal catalyst compositions
US6667274B1 (en) 1999-12-30 2003-12-23 Phillips Petroleum Company Polymerization catalysts
US6576583B1 (en) 2000-02-11 2003-06-10 Phillips Petroleum Company Organometal catalyst composition
US6583241B1 (en) 2000-03-20 2003-06-24 Chevron Phillips Chemical Company Lp Process for making MVTR resin
US6388017B1 (en) 2000-05-24 2002-05-14 Phillips Petroleum Company Process for producing a polymer composition
US6984698B2 (en) 2001-01-31 2006-01-10 Fina Technology, Inc. Polyethylene films for barrier applications
CA2490889C (en) 2002-06-27 2009-04-14 Pliant Corporation Lap sealable film with a peel layer
US6914113B2 (en) 2002-07-25 2005-07-05 Fina Technology, Inc. Film clarity and rheological breadth in polyethylene resins
US20060089253A1 (en) 2002-08-13 2006-04-27 Shahram Mihan Monocyclopentadienyl complexes
US7601655B2 (en) 2003-09-27 2009-10-13 Tactix Llc Engineered toweling
US7501372B2 (en) * 2003-11-21 2009-03-10 Chevron Phillips Chemical Company Lp Catalyst compositions for producing polyolefins in the absence of cocatalysts
US7214642B2 (en) 2004-04-22 2007-05-08 Chevron Phillips Chemical Company Lp Methods of preparing active chromium/alumina catalysts via treatment with sulfate
US7294599B2 (en) 2004-06-25 2007-11-13 Chevron Phillips Chemical Co. Acidic activator-supports and catalysts for olefin polymerization
US7163906B2 (en) 2004-11-04 2007-01-16 Chevron Phillips Chemical Company, Llp Organochromium/metallocene combination catalysts for producing bimodal resins
US20070007680A1 (en) 2005-07-05 2007-01-11 Fina Technology, Inc. Methods for controlling polyethylene rheology
US20070010626A1 (en) 2005-07-11 2007-01-11 Shankernarayanan Manivakkam J Polyethylene compositions
US7226886B2 (en) 2005-09-15 2007-06-05 Chevron Phillips Chemical Company, L.P. Polymerization catalysts and process for producing bimodal polymers in a single reactor
US7517939B2 (en) 2006-02-02 2009-04-14 Chevron Phillips Chemical Company, Lp Polymerization catalysts for producing high molecular weight polymers with low levels of long chain branching
CA2568454C (en) 2006-11-17 2014-01-28 Nova Chemicals Corporation Barrier film for food packaging
US20090035545A1 (en) 2007-07-30 2009-02-05 Fina Technology, Inc. Polyethylene films with improved bubble stability
US7884163B2 (en) 2008-03-20 2011-02-08 Chevron Phillips Chemical Company Lp Silica-coated alumina activator-supports for metallocene catalyst compositions
US7884165B2 (en) 2008-07-14 2011-02-08 Chevron Phillips Chemical Company Lp Half-metallocene catalyst compositions and their polymer products
US8828529B2 (en) 2010-09-24 2014-09-09 Chevron Phillips Chemical Company Lp Catalyst systems and polymer resins having improved barrier properties
US8501651B2 (en) 2010-09-24 2013-08-06 Chevron Phillips Chemical Company Lp Catalyst systems and polymer resins having improved barrier properties

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5418200A (en) * 1991-03-29 1995-05-23 Chevron Chemical Company Cyclopentadienyl group 6B metal α-olefin polymerization catalysts and process for polymerizing α-olefins
EP0620830B1 (en) * 1992-11-06 1997-04-23 Chevron Chemical Company ALPHA-OLEFIN POLYMERIZATION CATALYSTS COMPRISING SUPPORTED CYCLOPENTADIENYL GROUP 6b METAL OXO, THIO, IMIDO AND PHOSPHIDO COMPOUNDS AND PROCESS FOR POLYMERIZING ALPHA-OLEFINS
CN1989158A (en) * 2004-06-25 2007-06-27 切弗朗菲利浦化学公司 Polymerization catalysts for producing polymers with low levels of long chain branching

Also Published As

Publication number Publication date
WO2012040147A1 (en) 2012-03-29
US8501651B2 (en) 2013-08-06
BR112013006892A2 (en) 2016-06-28
CN103154048A (en) 2013-06-12
ES2677068T3 (en) 2018-07-27
EP2619235A1 (en) 2013-07-31
US20130225820A1 (en) 2013-08-29
CA2996547A1 (en) 2012-03-29
ZA201302163B (en) 2014-05-28
US20120077665A1 (en) 2012-03-29
CA2996547C (en) 2019-03-12
CA2812260C (en) 2018-07-24
US8703972B2 (en) 2014-04-22
CA2812260A1 (en) 2012-03-29
EP2619235B1 (en) 2018-04-25
BR112013006892B1 (en) 2020-12-08

Similar Documents

Publication Publication Date Title
CN103154048B (en) Catalyst system improves impervious fluoropolymer resin with having
CN103119070B (en) Antigravity system improves impervious fluoropolymer resin with having
CN102844341B (en) Catalyst composition for producing high mz/mw polyolefins
CN104004116B (en) Dual activator carried catalyst system
CN101935366B (en) Dual metallocene catalyst systems for decreasing melt index and increasing polymer production rates
CN102958948B (en) For producing the catalyzer of wide molecular weight distribution polyolefin when not adding hydrogen
CN103108894B (en) Its method of new catalyst system and preparation and use
CN102617759B (en) Mono-metallocene compound and carbon monoxide-olefin polymeric
CN102348725B (en) Catalyst and process for producing a polymer containing a high molecular weight tail
CN101910211B (en) Nano-linked metallocene catalyst compositions and their polymer products
CN103193913B (en) Produce the method compared with broad molecular weight distribution polymers with anti-copolymerization monomer distribution and low levels of long chain branches
CN102020729B (en) Silica-coated alumina activator-supports for metallocene catalyst compositions
CN101935367B (en) Hydrogen for controlling polymericular weight and hydrogen level in polymerization reactor removes the application of catalyzer
CN104418963A (en) Higher Density Polyolefins With Improved Stress Crack Resistance
CN104292368A (en) Methods for producing fluorided-chlorided silica-coated alumina activator-supports and catalyst systems containing the same
CN103848931A (en) Catalyst System With Three Metallocenes for Producing Broad Molecular Weight Distribution Polymers
CN104371050A (en) Cyclobutylidene-Bridged Metallocenes and Catalyst Systems Containing the Same
KR102509503B1 (en) Ziegler-Natta-Metallocene Dual Catalyst System with Activator-Support
CN101628243A (en) Half-metallocene catalyst composition and poly products thereof
CN105283472A (en) Activator-supports impregnated with group VIII transition metals for polymer property control
CN106459440A (en) High performance moisture barrier films at lower densities
CN103819587A (en) Metallocene and half sandwich dual catalyst systems for producing broad molecular weight distribution polymers
CN103140513A (en) Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects
CN101184782A (en) Catalysts for olefin polymerization
CN103930450A (en) Polymer compositions having improved barrier properties

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
REG Reference to a national code

Ref country code: HK

Ref legal event code: DE

Ref document number: 1185896

Country of ref document: HK

C14 Grant of patent or utility model
GR01 Patent grant
REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1185896

Country of ref document: HK